A novel laboratory methodology for analysing hot asphalt fumes from various paving materials is presented and evaluated. This method facilitates comparative assessments, aiming to enhance occupational safety for asphalt workers and ensure safe implementation of new paving materials. Comparative analyses of emissions to air were conducted on standard asphalt and rubber-modified asphalt at different temperatures. The temperature significantly influences PAH emissions. Rubber-modified asphalt demonstrated higher PAH emissions at equivalent temperatures compared to standard asphalt, predominantly naphthalene. Even heavier PAHs as benzo(a)pyrene were occasionally high. Notably, at recommended working temperatures the standard asphalt resulted in higher emissions, comprising heavier PAHs compared to rubber asphalt.