The Government Arts College for Women was established in 1966 with the main objective of providing higher education for Women of Thanjavur. The College was renamed as 'Kunthavai Naacchyiaar Government Arts College for Women' in memory of the illustrious Sister of Raja Raja Chola on the occasion of the 1000th anniversary celebration of the Coronation of the Great King of Thanjavur. The decision of the Government of Tamil Nadu has helped the women of Thanjavur who are otherwise tradition bound and were hesitant to go even to nearby places in pursuit of Higher Education.

The College was housed in the Thanjavur Palace premises itself in the beginning and in 1970 it was shifted to its own two storeyed building in a sprawling campus of 17.5 acres. When more academic programmes were introduced in the College, there was increased demand for space and subsequently, more buildings were constructed with generous grants from the Government of Tamil Nadu. The infrastructure has been further strengthened with the Constituency Development Fund received through the Member of Parliament and Member of Legislative Assembly. In order to meet the increased demand for space, the Tamil Nadu Government has sanctioned ₹ 31.9 Lakhs to the College for the construction of a building with 5 Classrooms in the year 2009. Recently Government has sanctioned ₹ 1,92,00,000/- for the construction of 31 classrooms. It is under construction.

Initially, when the college was started, only Pre University Courses were offered. Thereafter in 1969 the college was upgraded by introducing UG Courses in History and Chemistry. Later, from 1972 to 1999, the academic activity in the institution progressed in leaps and bounds with the addition of a series of UG Courses such as BA in Geography, English Literature, Ecnomics, Tamil Literature, UG Programme in Botany, Zoology, Physics, Mathematics, Computer Science and BCom Degree programme.

An impetus for higher education was given when the PG Programme in History, English Literature and Economics were introduced in the college during the years 1976, 1981 and 1998 respectively. Apart from these day College programmes, self-financing programme in UG Economics, English, Commerce and Tamil Literature were also introduced during the year 1993-1994.

UG Courses started in the year 1993 and the PG Courses started under the Self-financing scheme in 2004 were converted into the regular stream in 2005. Special Shift System was introduced in the year 2006 by the State Government Policy of educating more children with the available infrastructure. Additional sections were introduced in Mathmatics, Computer Science and Commerce. Later in 2007 two additional sections were introduced in Physics. BBA in retail management has been introduced in 2009.

The College which had a modest beginning with just three sections of Pre University Courses in 1966, presently has 14 Departments in the faculties of Arts, Science, Commerce and BBA offering 14 UG Programmes and 11 PG Programmes. It has faculty strength of 100 members of whom 62 have acquired PhD degree. In the meantime, the student strength of the College has increased from 260 to 4500. A majority of the students come from rural areas and are first generation learners. The academic, extra-curricular and extension programme are largely aimed at the personality development under the able leadership of several eminent lady academics who served as Principals of this College.

The College which was originally affiliated to Madras University, came under the jurisdiction of Bharathidasan University since 1982. It is now adjudged as one of the best Women's colleges in Tamil Nadu by the Directorate of Collegiate Education and stands second among the Government Colleges within the State based on the student strength. It has strong co-curricular and extra-curricular activities.