During her college days, composer Mithoon offered her to record the song "Javeda Zindagi" from Anwar (2007), marking her Hindi debut.

Rao rose to widespread prominence with the release of "Woh Ajnabee" from The Train (2007) and "Khuda Jaane" from Bachna Ae Haseeno (2008), the latter of which earned her a nomination for the Filmfare Award for Best Female Playback Singer.

[5] He taught Rao to understand the "nuances" of different ragas: "His method of teaching was casual and at the same time very effective because it was designed to pique my interest".

[5] Initially, she found herself struggling in "finding references" and meeting music composers since she was not "so active" in social networking media during the time.

[5] About her early days in the city, Rao said: "Jamshedpur is home for me but Mumbai with the people, the place, the pace everything has made a more patient person and a more hardworking artist I could ever be".

Though "Sehra" from the former met with negative reactions from music critics, both "Woh Ajnabee" and "Teri Tamanna" from the latter were well received; Raja Sen from Rediff.com praising Rao's "strong vocals" in particular.

[14] While shooting for Salaam-e-Ishq, music composer Shankar Mahadevan from the trio Shankar–Ehsaan–Loy suggested Rao's name to director Nikhil Advani, thus landing the song "Saiyaan Re".

[18] Rao's first release of 2008 came with Raghav Sachar-composed remix version of "Gup Chup" from One Two Three, followed by "Ek Lau" from Aamir, composed by Amit Trivedi.

[11] Apart from rendering "Main Sajda" for Anu Malik in Good Luck!, she was heard in a "faint alaap" at the beginning of the song "Koi Na Jaane" from Hijack, along with KK.

[25] In 2010, Rao collaborated with Pritam for the first time, and performed "Ittefaq Tu Nahin" for Mallika and "Dil Le Jaa" for Toh Baat Pakki!.

[29] She did playback for Bappi Lahiri in "Ankhiya Na Maar" of Apartment and performed two tracks for Lahore; Piyush Mishra's Sufi song "O Re Bande" and M.M.

[30] In the year, Rao made her Tamil music debut with the song "Oru Maalai Neram" from Yuvan Shankar Raja-composed Naan Mahaan Alla along with Javed Ali.

[citation needed] Rao collaborated with lyricist Neelesh Misra and composer Amartya Rahut and formed the Band Called Nine, which works for the traditional Indian craft of storytelling.

[36] Rao considered MTV Unplugged "very challenging" to do since she had to create a totally different version of songs and "present it to people, who have heard it earlier and liked it".

[36] After Ladies vs Ricky Bahl, Rao worked again with Salim–Sulaiman for "Jab Main Tumhare Saath Hun" from Jodi Breakers (2012).

[38] Apart from rendering "Yaariyaan" from Cocktail,[39] Rao teamed up with Trivedi in two other films, Ek Main Aur Ekk Tu and English Vinglish.

[42] The year concluded with Rao's collaboration with A. R. Rahman, by recording the track "Ishq Shava" from Jab Tak Hai Jaan, which was a fusion of Arabic and techno sounds.

[44] In the song, the singers recorded for actors whom they generally do the playback singing for, and Rao dubbed for Sonam Kapoor and Deepika Padukone.

[citation needed] Her next release, "Manmarziyaan" from Trivedi's Lootera was widely acclaimed by critics; while Filmfare's Devesh Sharma complimented Rao's "wistful rendering" in the song, Mohar Basu from Koimoi mentioned that she is "flawless" in her part.

[52] Similar was the case in her next release, the reprise version of "Le Chal Mujhe" from NH10, where she tried a "low octave" kind of voice texture for the song.

[51] Rucha Sharma from Daily News and Analysis affirmed that, Rao in her version "managed to outshine two most sought after singers, Chauhan and Singh".

[53] In 2016, Rao became the second Indian singer after Sharmistha Chatterjee who appeared with Mekaal Hasan Band, to have the honour of singing in the critically acclaimed musical show Coke Studio Pakistan.

"[59] Sharing the experience, she said that "[Coke Studio Pakistan] is a place where all the musicians are in an environment where they have their instruments, their space and the freedom to choose anything and convey it to the people in their own style; it's very powerful.

[62] She credited her music influences and training for the shaping of her voice and style of singing; "I have attempted diverse genres and have always tried to put out something new for audiences with every song".

[citation needed] After moving to Mumbai, Rao was succoured by Hariharan and Shankar Mahadevan whom she considers her as "constant source of inspiration".

[citation needed] Maintaining a healthy diet, Rao restricts too much sweet, and "strong smelling fruits" since she is "very sensitive" to odors.

[67] In an interview with Bombay Times about her wedding, Rao said, "We met three years ago on (music composer) Pritam's USA tour.

[70] She performed in Delhi at the "100 Pipers Play for a Cause" which is a musical extravaganza dedicated to raising funds for people affected by the Nepal earthquake.

[72] In May 2013, Rao performed in an event focused to create awareness about the effects and influence of tobacco and to raise funds for cancer patients.

[73] In October 2014, Rao took part in the musical concert held in New Delhi for raising funds for the flood affected people of Assam.