Background Atmospheric levels of polycyclic aromatic hydrocarbons (PAHs) have been monitored in many companies since 1940. Because of the use of respiratory protective equipment (RPE) and cutaneous absorption, the measurement of urinary 1-hydroxypyrene (1-OHP), metabolite of pyrene (Pyr), and, more recently, 3-hydroxybenzo[a]pyrene (3-OHBaP), metabolite of benzo[a]pyrene (BaP), has been carried out to assess PAH exposure and estimate health risks. Objectives This study aimed to investigate the agreement between 523 air and biological levels recorded in the Exporisq-HAP database by taking into account the effectiveness of RPE. Methods The agreement/consistency between 523 air and biological exposure levels was assessed by estimating and comparing the probability of exceeding French limit values (LVs) for both BaP and 3-OHBaP and ACGIH LV for 1-OHP, respectively. PAH airborne levels (wPAHs) were weighted by an assigned protection factor (APF) depending on the type of mask worn by workers, while urinary 1-OHP concentrations were adjusted with the wBaP/wPyr ratio of each industrial sector (wadj1-OHP). Results Within occupational groups, there was an overall agreement between airborne PAH levels and urinary biomarker concentrations. A clear dichotomy was found between “petroleum-derived” and “coal-derived” groups, with much higher exposures in the latest group despite the use of RPEs by two-thirds of the workers. The type of RPE varied from one plant to another, which underlines the importance of taking into account their effectiveness. The analysis of urinary 3-OHBaP was not relevant for low PAH exposure levels. In addition, this biomarker underdiagnosed the exceedance of LV relative to BaP levels for 6% of “coal-derived” groups. Conclusions The use of urinary wadj1-OHP seemed to be more protective to assess the exceedance of LVs than those of urinary 3-OHBaP and air wBaP, but adjustment of the 1-OHP concentration by the BaP/Pyr ratio requires air sampling due to highly variable ratios observed in the studied occupational groups.