Malini was born in a Tamil-speaking Iyengar family to her mother Jaya Lakshmi Chakravarti, a film producer and VSR Chakravarti. She attended the Andhra Mahila Sabha in Chennai. Malini studied at DTEA Mandir Marg and in grade 12 left to begin her acting career. She got married with Dharmendra in 1979. Malini's first film with Dharmendra was Sharafat. Malini and Dharmendra have two children, Bollywood actress Esha Deol and Ahana Deol. Malini performed with Dharmendra in twenty-eight movies. Malini is a trained Bharatanatyam dancer. Her daughters Esha Deol & Ahana Deol are also trained Odissi dancers. Dharmendra was already married at the time and had children, two of whom are Bollywood actors Sunny Deol and Bobby Deol. Malini's niece is actress Madhoo. Malini was a supporting artiste in Idhu Sathiyam. In Johnny Mera Naam, Malini took a lead role and she took other challenging roles. In 1972, Malini played opposite Dharmendra and Sanjeev Kumar in Seeta Aur Geeta. Within four years of making her debut, Malini was an established lead actress in Bollywood and classical dancer. After her marriage, Malini made films including Kranti, Naseeb, Satte Pe Satta , Rajput, and Ek Nai Paheli. She directed the film Dil Aashna Hai with Divya Bharti and Shahrukh Khan in the leading roles. After taking a break from films for a number of years, Hema made a comeback with Baghban in 2003. Malini is a supporter of the animal rights organization, PETA India. Malini won the title of "PETA Person of the Year. Malini has appeared in television series such as Jai Mata Ki.
In 1999, Malini campaigned for the Bharatiya Janata Party (BJP) candidate, Vinod Khanna, a former Bollywood actor, in the Lok Sabha Elections in Gurdaspur, Punjab. From 2003 to 2009, she served as an MP to the upper house of the Rajya Sabha, having been nominated by the President of India, A. P. J. Abdul Kalam. In March 2010, Malini was made general secretary of the BJP, and in February 2011, she was recommended by Ananth Kumar, the party general secretary. Malini was then elected to the Lok Sabha. Malini owned the editorship of New Woman, a Hindi woman's magazine. In 2000, Malini was appointed as the first female chairperson of the National Film Development Corporation for a term of three years. Malini also became a brand ambassador for Pothys, a textile showroom in Chennai.