A plethora of chemicals are released into the air during combustion events, including a class of compounds called polycyclic aromatic hydrocarbons (PAHs). PAHs have been implicated in increased risk of cancer and cardiovascular disease, both of which are disease endpoints of concern in structural firefighters. Current commercially available personal protective equipment (PPE) typically worn by structural firefighters during fire responses have gaps in interfaces between the ensemble elements (e.g., hood and jacket) that allow for ingress of contaminants and dermal exposure. This pilot study aims to use silicone passive sampling to assess improvements in dermal protection afforded by a novel configuration of PPE, which incorporates a one-piece liner to eliminate gaps in two critical interfaces between pieces of gear. The study compared protection against parent and alkylated PAHs between the one-piece liner PPE and the standard configuration of PPE with traditional firefighting jacket and pants. Mannequins (n = 16) dressed in the PPE ensembles were placed in a Fireground Exposure Simulator for 10 min, and exposed to smoke from a combusting couch. Silicone passive samplers were placed underneath PPE at vulnerable locations near interfaces in standard PPE, and in the chamber air, to measure PAHs and calculate the dermal protection provided by both types of PPE. Silicone passive sampling methodology and analyses using gas chromatography with mass-spectrometry proved to be well-suited for this intervention study, allowing for the calculation and comparison of worker protection factors for 51 detected PAHs. Paired comparisons of the two PPE configurations found greater sum 2-3 ring PAH exposure underneath the standard PPE than the intervention PPE at the neck and chest, and at the chest for 4-7 ring PAHs (respective p-values: 0.00113, 0.0145, and 0.0196). Mean worker protection factors of the intervention PPE were also greater than the standard PPE for 98% of PAHs at the neck and chest. Notably, the intervention PPE showed more than 30 times the protection compared to the standard PPE against two highly carcinogenic PAHs, dibenzo[a,l]pyrene and benzo[c]fluorene. Nine of the detected PAHs in this study have not been previously reported in fireground exposure studies, and 26 other chemicals (not PAHs) were detected using a large chemical screening method on a subset of the silicone samplers. Silicone passive sampling appears to be an effective means for measuring dermal exposure reduction to fireground smoke, providing evidence in this study that reducing gaps in PPE interfaces could be further pursued as an intervention to reduce dermal exposure to PAHs, among other chemicals.