Polycyclic aromatic hydrocarbons (PAHs) are compounds with high carcinogenic potential, produced during incomplete combustion. Certain professions, such as firefighting, expose workers to significant levels of PAHs during their operations, making it essential to investigate sampling protocols to evaluate their exposure in the work environment.This study presents a non-destructive and cost-effective sampling method for monitoring PAHs in firefighters’ personal protective equipment (PPE) and intervention vehicles. Sampling was conducted using three isopropanol wipes per collection zone, with comprehensive validation trials ensuring the method’s effectivenes. The method was tested under both natural contamination and spiking scenarios, showing similar results in both protocols.Analysis of contaminated PPE revealed significant PAH contamination in specific zones, such as gloves, lower back sleeves, and knees, due to direct exposure to flames and smoke during firefighting, with the highest concentrations in the outer and moisture layers. The cleaning efficacy of PPE was also evaluated employing specific washing machines, showing substantial reductions in PAH levels of approximately 76%. Additionally, non-targeted analysis detected organophosphate flame retardants (OPFRs) and furans, suggesting broader utility for environmental monitoring. This comprehensive approach improves the accessibility of chemical exposure studies in high-risk professions, contributing to better protective measures and occupational health and safety.