Objective: Investigate the independent relationship of multiple exposures to work characteristics and occupational risks factors in the occurrence of accidents at work and on the way to work. Methods: A cross-sectional study from 47,629 participants of the Brazilian National Health Survey. The association magnitudes were estimated by Odds Ratio and its respective 95% confidence interval. Results: Exposure to intense noise, biological materials, work experience of 40 years or more and intense physical exertion were independently associated with accidents at work. Only exposure to intense noise and activity with effort 6 to 7 times per week remained independently associated with accidents on the way to work. Conclusion: This research contributed to highlight the effects of multiple exposures at work responsible for the increasing of accidents at work and on the way to work in Brazil.