Breast cancer is the most frequent tumor in women worldwide, although well-established risk factors account for 53%–55% of cases. Therefore, other risk factors, including environmental exposures, may explain the remaining variation. Our objective was to assess the relationship between risk of breast cancer and residential proximity to industries, according to categories of industrial groups and specific pollutants released, in the context of a population-based multicase-control study of incident cancer carried out in Spain (MCC-Spain). Using the current residence of cases and controls, this study was restricted to small administrative divisions, including both breast cancer cases (452) and controls (1511) in the 10 geographical areas recruiting breast cancer cases. Distances were calculated from the respective woman's residences to the 116 industries located in the study area. We used logistic regression to estimate odds ratios (ORs) and 95% confidence intervals (95%CIs) for categories of distance (between 1 km and 3 km) to industrial plants, adjusting for matching variables and other confounders. Excess risk (OR; 95%CI) of breast cancer was found near industries overall (1.30; 1.00–1.69 at 3 km), particularly organic chemical industry (2.12; 1.20–3.76 at 2.5 km), food/beverage sector (1.87; 1.26–2.78 at 3 km), ceramic (4.71; 1.62–13.66 at 1.5 km), surface treatment with organic solvents (2.00; 1.23–3.24 at 3 km), and surface treatment of plastic and metals (1.51; 1.06–2.14 at 3 km). By pollutants, the excess risk (OR; 95%CI) was detected near industries releasing pesticides (2.09; 1.14–3.82 at 2 km), and dichloromethane (2.09; 1.28–3.40 at 3 km). Our results suggest a possible increased risk of breast cancer in women living near specific industrial plants and support the need for more detailed exposure assessment of certain agents released by these plants.