(1) Background: Highway toll plazas are environments impacted by atmospheric pollutants that may affect workers’ health. However, there are still few studies on these environments. This study evaluated particulate matter (PM) concentrations by size fraction (PM_10–9.0 to PM_0.43) and associated arsenic (As), cadmium (Cd), chromium (Cr), copper (Cu), manganese (Mn), nickel (Ni), lead (Pb) and vanadium (V) at two toll plazas in Brazil. (2) Methods: PM and trace element concentrations were compared between dry and rainy seasons, and a health risk assessment was conducted for toll collectors based on inhalation exposure. (3) Results: PM_10–2.5 concentrations ranged from 31.8 to 360 µg m⁻³ in the dry season and from non-detectable to 287 µg m⁻³ in the rainy season. PM_2.5 levels varied between 14.9 and 150 µg m⁻³ (dry) and 3.46–174 µg m⁻³ (rainy). Although trace element concentrations were within Occupational Safety and Health Administration (OSHA) limits, the hazard quotient (HQ) for manganese and arsenic exceeded unity (HQ > 1), indicating potential health risks. (4) Conclusions: These findings suggest that toll plaza workers may experience increased inhalation-related risk under the exposure assumptions used. Improved ventilation and protective measures, including the use of protective screens, are recommended to reduce occupational exposure.