Devayani has been married twice. Her first marriage was to film director K. S. Ravikumar, with whom she has a daughter named Keerthana. However, the couple divorced due to personal reasons.

In 2002, Devayani married actor Jai, whom she met on the sets of a film. The couple has a daughter named Niva. Their marriage, too, ended in divorce, reportedly due to differences.

In the pantheon of 1990s and early 2000s Tamil cinema, few actresses captured the nuance of a woman in love quite like Devayani. While she was never one to court off-screen controversies or headline tabloid rumors about her personal life, her professional romantic pairings became the stuff of legend. For over a decade, Devayani was the gold standard for the "girl next door"—accessible, emotionally resonant, and possessing a unique ability to oscillate between bubbling teenage infatuation and gut-wrenching marital tragedy.

This article does not dissect mere gossip; instead, it explores the cinematic relationships and romantic storylines that defined Devayani’s career. From the comedic courtships with the "Ultimate Star" to the tragic, tear-jerking sagas that still haunt social media reels, Devayani’s filmography is a masterclass in romantic storytelling.

Devayani had a knack for working with actors who forced her to play complex, often melancholic roles.