As the Fire Service becomes more aware of the potential health effects from occupational exposure to hazardous contaminants, personal protective equipment (PPE) manufacturers, and fire departments have responded by developing and implementing improved means of firefighter protection, including more frequent laundering of PPE after exposures. While laboratory testing of new PPE designs and the effect of laundering on PPE fabric provides a useful way to evaluate these approaches, laboratory scale testing does not necessarily translate to full garment protection. Utilizing a fireground smoke exposure simulator, along with air and/or filter-substrate sampling for polycyclic aromatic hydrocarbons (PAHs) and benzene, this pilot study tested the chemical-protective capabilities of firefighting PPE of different designs (knit hood vs. particulate-blocking hood, turnout jacket with zipper closure vs. hook & dee closure), including the impact of repeatedly exposing and cleaning (through laundering or decontamination on-scene) PPE 40 times. Overall, PAH contamination on filters under hoods in the neck region were higher (median PAHs ¼ 14.7 mg) than samples taken under jackets in the chest region (median PAHs ¼ 7.05 mg). PAH levels measured under particulate-blocking hoods were lower than levels found under knit hoods. Similarly, zippered closures were found to provide a greater reduction in PAHs compared to hook & dee closures. However, neither design element completely eliminated contaminant ingress. Measurements for benzene under turnout jackets were similar to ambient chamber air concentrations, indicating little to no attenuation from the PPE. The effect of laundering or onscene decontamination on contaminant breakthrough appeared to depend on the type of contaminant. Benzene breakthrough was negatively associated with laundering, while PAH breakthrough was positively associated. More research is needed to identify PPE features that reduce breakthrough, how targeted changes impact exposures, and how fireground exposures relate to biological absorption of contaminants.