Born on July 27, 1963, in Thiruvananthapuram, Kerala, into a family of musicians, Chithra’s talent was recognized and nurtured from an early age by her father, the late Krishnan Nair. He was also her first guru (teacher). Chithra received her extensive training in Carnatic music from Dr. K. Omanakutty, and got a Masters in Music from the University of Kerala. She was selected for the National Talent Search Scholarship from the Central Government from 1978–1984. She is married to Vijayashankar, an engineer and businessman. Their only daughter Nandana passed away aged 8, in an accident in April 2011.

Chitra was introduced to Malayalam playback by M. G. Radhakrishnan in 1979 and went on to become a regular singer for many Malayalam musicians, including Raveendran. Attahasam, Snehapurvam Meera and Njaan Ekananu were the first few films which she recorded her songs. She also performed live concerts with K. J. Yesudas in India and abroad and that was a turning point in her career. Veteran music directors such as Raveendran, Shyam, Jerry Amaldev, Mohan Sithara, Kannoor Rajan and Johnson also helped her move up in her career ladder. She made her debut in the Tamil film industry through the song "Poojaikketha Poovithu" from the film Neethana Antha Kuyil, which was composed by Ilaiyaraaja. She was given the title Chinnakuyil after singing the song "Chinna Kuyil Paadum" from the 1985 released film Poove Poochudava. Director Fazil cast her for this song after Ilaiyaraaja got impressed with her song sung in original version in Malayalam for the film Nokkethadhoorathu Kannum Nattu in 1984 directed by himself.

By the mid-eighties, she became the most sought after female singer in Malayalam and Tamil. She recorded many hit songs for the most famous composers in Malayalam and numerous songs for Ilaiyaraaja in Tamil. She has been acredited as the only female singer to have sung the maximum number of songs for the Academy Award winning composer A. R. Rahman for his Tamil film songs. She also sang for veteran composers such as G. Devarajan, M. S. Viswanathan, K. V. Mahadevan, Ouseppachan, Deva, Vidyasagar, Bharadhwaj, Chakravarthy, M. Jayachandran, M.G.Sreekumar, M. M. Keeravani, Hamsalekha, Sharreth, Raj-Koti, Rajan-Nagendra, S. A. Rajkumar, Mani Sharma, Harris Jayaraj, Devisri Prasad and many other south Indian music directors.

Chitra has recorded many memorable Hindi songs for various music directors in Bollywood, namely A. R. Rahman, Anand-Milind, Anu Malik, Rajesh Roshan, Viju Shah, Laxmikant-Pyarelal, Naushad, Shankar-Ehsaan-Loy, Jatin-Lalit and many others. She also recorded the Hindi versions of her own Tamil songs sung for A. R. Rahman.

Apart from playback singing, she also appeared among the panel of judges in the singing reality Television shows at Kerala (Idea Star Singer) and Tamil Nadu (Airtel Super Singer Junior).

Chithra, along with a Kerala based satellite channel, Asianet Cable Vision (ACV), has jointly launched a fund raising organization Sneha to raise funds for the betterment and welfare of long forgotten and aged musicians who have lost their careers to the emerging technological elements in the music industry. She has launched this organization on the occasion of her completion of three decades in the music playback industry. Chithra has remarked that the fund would provide help to the musicians with financial impediments and those suffering from health problems.

A cultural event named Chitra Pournami was held on 15 February 2011 at Thiruvananthapuram to celebrate the 30 glorious career years of Chithra and also to officially launch this organization. The who's who of South Indian music industry attended the event and felicitated Chithra with a Tamboora instrument. The prominent personalities being K. J. Yesudas, V. Dakshinamurthy, Sreekumaran Thampi, P. Susheela, Hariharan, M. G. Sreekumar, Sharath, Sujatha Mohan, Unni Menon, Minmini among others felicitated Chithra and praised her noble cause and intentions to help for the ailing musicians.