This study investigated whether the individual and combined effects of using biomass energy and living in the neighborhood of a cement plant were associated with the risk of COPD and respiratory symptoms among Congolese women. A total of 235 women from two neighborhood communities of a cement plant participated in this cross-sectional study. Participants were classified into the more exposed group (MEG = 137) and a less exposed group (LEG = 98), as well as into biomass users (wood = 85, charcoal = 49) or electricity users (101 participants). Participants completed a questionnaire including respiratory symptoms, sociodemographic factors, medical history, lifestyle, and household characteristics. In addition to spirometry performance, outdoor PM2.5 (μg/m3) was measured. Afternoon outdoor PM2.5 concentration was significantly higher in MEG than LEG (48.8 (2.5) μg/m3 vs 42.5 (1.5) μg/m3). Compared to electricity users, wood users (aOR: 2.6, 95%CI 1.7; 5.9) and charcoal users (aOR: 2.9, 95%CI 1.4; 10.7) were at risk of developing airflow obstruction. Combined effects of biomass use and living in the neighborhood of a cement plant increased the risk of COPD in both wood users (aOR: 4, 95%CI 1.3; 12.2) and charcoal users (aOR: 3.1, 95%CI 1.7; 11.4). Exposure to biomass energy is associated with an increased risk of COPD. In addition, combined exposure to biomass and living near a cement plant had additive effects on COPD.