Objectives: The objective of the work was to analyze the impact of selected factors concerning the use and maintenance of firefighters’ protective clothing worn during rescue operations on the hazard of contamination by chemical substances. Material and Methods: The participants were firefighters (N = 688) from rescue and firefighting units of the State Fire Service in Poland, aged <30, 31–40, 41–50 or >60 years, with different seniority: up to >21 years of service. The survey questionnaire developed by the authors was used. The questionnaire was available online. The Statistica 10.0 statistical package using the χ² test was applied in the analysis of the significance of the results. Results: As reported by the vast majority (>60%) of the firefighters, the maintenance was carried out after recording an average or a high level of contamination. It was pointed out that removal of the contaminants from protective clothing was difficult (83%). The surfaces of the legs and sleeves of protective clothing were the most contaminated areas. A feeling of discomfort was observed (90%) after returning from firefighting operations due to fire, smoke, or combustion residues. Conclusions: It is necessary to conduct training and information actions concerning the use and maintenance of protective clothing and the harmfulness of chemicals contaminating the garments used by firefighters. Int J Occup Med Environ Health. 2022;35(2):235–48