She played the main protagonist Nandini, a Gujarati woman who is forced into wedlock (with Devgan's character) despite being in love with another man (played by Khan).
Bhansali cast Rai after he met her at the screening of a film and was impressed with her eyes.
The film was a critical and commercial success and earned Rai positive comments from critics; a review carried by The Indian Express summarised, "Attacking her role with just the perfect dollop of innocence, Aishwarya does full justice to her part, and matches up perfectly to Tabu." Rai next starred alongside Shah Rukh Khan and Chandrachur Singh in the action drama Josh.
She portrayed Shirley Dias, the twin sister of Khan's character who falls in love with his arch enemy's brother (played by Singh).
In 2003, she was the first Indian actress to be a jury member at the Cannes Film Festival.
In 1993, Rai gained huge public recognition for her appearance in a Pepsi commercial with actors Aamir Khan and Mahima Chaudhry.
Directed by Rajiv Menon, the film also starred Tabu, Mammooty and Ajith Kumar in prominent roles.
She played Madhumita, a young woman who accompanies her ailing grandmother to the United States to seek medical attention.
Rai's greatest commercial successes have been the romance Mohabbatein (2000), the adventure film Dhoom 2 (2006), the historical romance Jodhaa Akbar (2008), the science fiction film Enthiran (2010), and the romantic drama Ae Dil Hai Mushkil (2016).
Rai married actor Abhishek Bachchan in 2007 with whom she has one daughter.
Her first commercial success was the Tamil romantic drama Jeans (1998), following which she achieved wider success and won two Best Actress awards at Filmfare for her performances in Hum Dil De Chuke Sanam (1999) and Devdas (2002).
Rai garnered critical appreciation for portraying a passionate artist in the Tamil romance Kandukondain Kandukondain (2000), Tagore's heroine, Binodini, in the Bengali film Chokher Bali (2003), a depressed woman in the drama Raincoat (2004), Kiranjit Ahluwalia in the British drama film Provoked (2006), as a nurse in the drama Guzaarish (2010) and as a justise-seeking sister in the biographical drama Sarbjit (2016).