The firefighting protective suits (FPSs) of firefighters at fire scenes affect their health and safety. However, the association between firefighters’ health awareness of occupational exposure risks and the FPS use, washing and management remains unclear. Therefore, this study aimed to evaluate the association between firefighters’ health awareness of occupational exposure risks and their recognition, behaviors regarding the use, washing and management of FPSs. This study design is a cross-sectional study and used a web-based survey of the Seoul Metropolitan Government’s electronic survey system. The survey was conducted on metropolitan firefighters performing shift work in charge of fire and rescue work for 21 days from 1 to 22 April 2019, with 1097 (40.3%) respondents. Characteristics of FPS use, washing and management and the association between thoughts and behaviors thereof and health awareness of occupational exposure risks were evaluated. Data of 1097 firefighters were analyzed using the SAS 9.4 statistical package, chi-square test and logistic regression analysis. Firefighters’ fire scene awareness rate of possible carcinogens was 94.4%. There was an association between public health thinking of occupational exposure risks and the correct use of an FPS for one’s own safety (AOR 1.97. 95% CI 1.02–3.80). However, no association was shown between correct FPS use (AOR 1.49, 95% CI 0.48–4.59), washing (AOR 2.50, 95% CI 0.93–6.68) and management (AOR 1.38, 95% CI 0.75–2.50) behaviors. This study analyzed the relationship between the use, washing and management of personal protective equipment called firefighting clothing and firefighters perceived occupational exposure risks. This study found an association between the health awareness of occupational exposure risks and recognition of the correct use of FPSs at fire scenes but not between using, washing and managing behaviors of FPSs. This study is the first to analyze the relationship between firefighting clothing and occupational health awareness level. The results confirm that future interventions are required to help firefighters practice desirable behaviors toward FPSs and provided evidenced data for preventing occupational diseases among firefighters. Therefore, this study can be used to develop a firefighter occupational health curriculum and establish health and safety plans from mid- to long-term perspectives for firefighters’ safety against occupational exposure risks.