Rajah Serfoji Government College (Autonomous) was named after Rajah Serfoji who was known for his scholarship and interest in Science and Arts subjects, as Rajah Serfoji College. The college was started temporarily on 23.06.1955 in Sangeetha Mahal of the Palace Complex of Thanjavur with one hundred and twenty students in intermediate class in groups I and III in part III. The former Governor of Tamilnadu, Honorable Sri. Prakasa officially inaugurated the college on 04.07.1955. The Rotary Club of Thanjavur then donated 156 acres of land for constructing buildings for the college. As per the stipulations of the Rotary Club of Thanjavur, when Thanjavur Medical College was started, 97 acres were transferred to it in 1960. The foundation stone was laid for the new premises for the college, in the remaining 69 acres by the then Finance Minister Honorable Sri. C. Subramaniam on 24.02.1956. On 04.11.1956, the Chief Minister Honorable Sri. Kamaraj inaugurated the new premises and the college was shifted to the new building.

In 1956, P.U.C. and Under Graduate Degree courses in Physics, Mathematics, and Economics were started. B.Sc. Zoology was started in June 1960 and B.Sc. Chemistry started in July 1961. With the consent of the university, girls were admitted in P.U.C and degree courses from 1960-1961. In April 1955, Madras High Court permitted the college to get a donation of Rs.3.5 lakhs from Kalimedu Chathram Funds. Half of this amount was utilized to build hostels in the name of the prime donor of the said Trust Sri. Naranappaiar. The rest of the amount was kept as principal amount; the interest accrued on the principal amount was utilized to provide free boarding and lodging facilities to the students. Sri. R. Arunachalam of Alivalam donated an amount of Rs.30,000/- for the students' free boarding hostel. The non-residential students' centre was completed in 1961-62. In the same year hostel buildings were also completed. From 1962-63 the auditorium, carpentry section, paper-making section, electronic section and photographic section were started. In 1964-65 an examination hall was completed and was brought into use. On 01.04.1965, the Government of Tamil Nadu took over the administration of the college. In July 1968 degree courses commenced in the evening college. Tamil medium was introduced in the Arts sections of P.U.C in June 1967, in the science sections of PUC in June 1968 and in degree courses in June 1969. Further in June 1969,B.Com degree course was started. M.A Economics and M. Sc. Mathematics courses were then started in the years 1970 and 1971 respectively.

The College has produced a great number of scholars, industrialists, politicians etc. Many of its alumni are occupying very high positions and are contributing to the uplift of the Nation. This college has the unique distinction of producing first-generation graduates and postgraduates. The M.Com course was introduced in the college in the year 2002. Rajah Serfoji Government College, being the biggest affiliated government college, as per the Tamil Nadu Government's policy, became the constituent College of Bharathidasan University, Tiruchirapalli. In 2003 two undergraduate, BBA and B. Sc. (Bio-Chemistry) and two post-graduate courses M. Sc. (Animal Science) and M.A. (English Literature) were started.

The college was conferred with autonomy status on September 2004. In the same academic year 2004-05 several new programs namely BBA, B. Sc. Computer Science, M.C.A. programs were started along with two additional PG programs namely M. Sc. Chemistry and M. Sc. Mathematics. The college introduced the Choice Based Credit System in the academic year 2005-06 for the PG programs and 2006-07 for all the UG programs. Every year around 1500 student are admitted to several UG and PG courses with extremely low fees, after admission, the mentors obtain the details from the students and assess the academic and other needs of these students, and initiates appropriate measures. The financial initiatives include the provision of scholarships and other concessions like free buses, and free hostel facilities provided to all deserving students from the disadvantaged sections.

In addition, the eligible students are forwarded for farmers' scholarships, single child scholarships, Tamil medium scholarships, scholarships for girls (Moovalur Ramamirtham Ammaiyar Scheme) Rs.1000 for eligible girl students, and first-generation scholarships. Even though it is a government college, through the endowment, scholarships and endowment prizes are provided to the meritorious students who excel in sports and cultural activities. Students facing difficulties in performing well in academic endeavors are provided special assistance in the form of special classes and remedial classes

Mentoring: Monitors the progress of the students based on their performances in the CIA components

Remedial Classes: Based on the performance of the students in the odd semester, the students are shortlisted for remedial classes in core and allied courses. Special Remedial classes are taken for SC/ST students.

Counseling: Students suffering from emotional distress and cultural shock are given necessary counseling and support through trained faculty members of the departments

In addition, the department societies and forums offer ample opportunities to sharpen their skills and talents to enhance their career. Internal Compliance Committee deal with their grievances instantaneously and they get placements through campus interview. The library and the digital library with longer opening hours (9.00 am to 4.00 pm) with free internet facilities give a wonderful opportunity to learn the subject and additional readings. The students are given opportunities to develop the skill to achieve the goals. The students with fine arts skills are groomed by the Fine Arts club. So, the students would certainly identify their potential and enrich their unique skill or multitasking skills for developing their careers. Every year number of students got placement in Government and non-government services. Every year students of our college have got a placement in the rank holders list of Bharathidasan University. So, we believe that we perform well towards our vision “To enrich, explore, enhance, experiment and excel in the higher education of our students and create opportunities to succeed” and reaching the mission “To encourage every student’s ability to grow in his/her field of capability”.