Since the beginning of the HIV/AIDS epidemic in India, pregnant women attending antenatal clinics (ANC) have been considered as a low HIV risk population. Yet, a substantial proportion of new HIV infections are occurring among stable heterosexual couples. This paper sought to investigate the proportion and profile of women who, within the low-risk population, are potentially at higher risk of HIV infection. HIV risk perception of pregnant women enrolled within the ANRS 12127 Prenahtest trial was described and associated socio-behavioral characteristics, husband's characteristics, and HIV-related characteristics were analyzed using univariate and multivariate logistic regression models. Among 484 women enrolled, baseline data were collected for 479 women and 460 women with completed data were considered for the present analysis (96%). Eighty-nine (19.4%) women perceived themselves at risk of HIV. Women with educational level <11years (Adjusted Odds Ratio, AOR = 2.4 [CI = 1.28-4.53]), who stayed in joint families (AOR = 1.89 [CI = 1.12-3.12]), who had experienced insult or hurt from the partner (AOR = 1.91 [CI = 1.11-3.27]) and whose partner were alcoholic (AOR = 2.19 [CI = 1.31-3.66]) were significantly more likely to perceive themselves at risk of HIV. Women who had heard about sexually transmitted infections were also more likely to report HIV risk perception (AOR = 3.36 [CI = 1.83-6.18]). Substantial proportion of women (one out of five) perceived themselves at risk of HIV and most of these have reported some form of vulnerability in their couple relationship such as intimate partner violence, alcoholic partner, lack of communication, and spaces for communication with partner. Though awareness and knowledge is the first step for prevention, considering the vulnerabilities associated with HIV risk perception, HIV prevention interventions in India should target overall sources of vulnerability to HIV. Targeted risk reduction for women in ANC should be considered for primary HIV prevention among couples.