Contaminants deposited on the firefighter protective clothing increase the risk of carcinogenesis by transdermal absorption. The effects of the inclination angle, waterproof grade, and fabric structure of the flame retardant outer layer of firefighting protective clothing on polycyclic aromatic hydrocarbon (PAH) contamination and laundering were studied by simulating smoking exposure. The permeation and transmission process of PAHs in multilayered assemblies were investigated. Results showed that the adsorption capacity of soot and PAH contamination on fabric with a water repellent finish relatively increased, and outer layer absorbed more PAHs at 180° compared to other inclination angles. The fabric structure with single layer had a strong adsorption capacity and low removal capacity for PAHs. The highest amount of PAH contaminant was found in the moisture barrier layer, and the removal rate (44.7%) was much lower than that of the outer layer cleaned through conventional laundering (91.3%). The research can better provide scientific support for pollution control and clothing cleaning in the actual firefight.