Devoleena was born on 22 August 1990 in Sivasagar, Assam, India into an Assamese family. She lost her father during her childhood. She lives in Mumbai with her mother and her younger brother. She completed her schooling from GBME School, Sivasagar, Assam and did her graduation in Commerce (Accountancy Honours).
In 2012, Bhattacharjee was cast overnight as the female lead Gopi Modi in Star Plus's drama Saath Nibhaana Saathiya after Giaa Manek, who previously played the role, was ousted from the series. In 2014 and again in 2016, she contemplated on quitting the show due to the frequent time leaps. Nevertheless, she continued to be a part of the show and in 2017, Devoleena completed five successful years of playing the protagonist. The show ended on 23 July 2017 after doing well for seven years. In June 2017, she had undergone a backbone surgery for an injury that took place on the sets of the show in 2013.
In January 2016, Devoleena informed the media that the sets of Saath Nibhaana Saathiya were haunted. She stated that the supernatural activities occurring on the sets had a negative influence on the cast and crew. In the same month, Devoleena landed in another controversy with Vishal Singh, an actor from the same show who plays the role of Jigar. The actors had an infamous showdown over her misbehaviour with senior actress Vandana Vithlani, who plays the role of Urmila in the show. However, they settled their differences after a few months.
In October 2016, Devoleena accused actress Utkarsha Naik, who played the role of Pramila in the same show of kidnapping her dog 'Jugnu' from the sets. She could not find her pet anywhere and for that reason she filed a complaint against her to PETA. She said,
“Yes, I am filing a complaint against Utkarsha, I think she is the one who is behind missing of Jugnu. Utkarsha was the one who took Jugnu in her car. And she was very obsessive about him. I am confident that it's Utkarsha who has done this thing. I am going to file a complaint against her in PETA.”
In March 2018, Devoleena's bank account was hacked.
↑Gopi bahu replaced overnight! (8 June 2012). “Giaa Manek, better known as Gopi bahu from the serial Saath Nibhana Saathiya, has been replaced overnight thanks to her decision to participate in the upcoming dance reality show Jhalak Dikhhla Jaa on a rival channel […] Now there's a new Gopi bahu on TV—Devoleena Bhattacharjee.”