Recently, in developing countries, polycyclic aromatic hydrocarbons (PAHs) have been considered contaminants of grave concern for women and children. Therefore, the aim of this study was twofold: (1) evaluate exposure assessment to PAHs using urinary 1-hydroxypyrene (1-OHP) as an exposure biomarker and (2) perform a health risk assessment in women from four different high risk scenarios in Mexico. From 2012 to 2013, in a cross-sectional study, we evaluated a total of 184 healthy women from the following scenarios: (A) indoor biomass combustion site (n = 50); (B) brick manufacturing site using different materials such as fuel sources (n = 70); (C) industrial site (n = 44); and (D) high vehicular traffic site (n = 20). 1-hydroxypyrene (1-OHP) was quantified using a high-performance liquid chromatography (HPLC) technique. Afterward, a probabilistic health risk assessment was performed (Monte Carlo analysis). Mean urinary 1-OHP levels found were 0.92 ± 0.92; 0.91 ± 0.83; 0.22 ± 0.19; and 0.14 ± 0.17 μg/L for scenario A, B, C, and D, respectively. Then, based on the measured urinary 1-OHP levels, the estimated median daily intake doses of pyrene were calculated: 659, 623, 162, and 77.4 ng/kg/day for the women participating in the study living in areas A, B, C, and D, respectively, and finally, the hazard quotient (HQ) was calculated (22 ± 21, 21 ± 20, 5.5 ± 5.5, and 2.6 ± 3.5; for areas A, B, C, and D, respectively), high health risk was noted for the women living in the studied communities. The data shown in this study (exposure levels to PAHs and health risk assessment) made it reasonable to conclude that the exposure levels found have a significant potential for generating adverse effects on human health in the studied scenarios.