Asphalt fumes released during pavement construction posed a threat to human health and environment. In this study, 9,10-dihydro-9-oxa-10-phosphorophenanthrene-10-oxide (DOPO) was used as a reactive fumes suppressant to reduce the asphalt fumes emission. The volatilization behavior of DOPO modified asphalt (DOPO-Asphalt) was investigated through thermogravimetric analysis, volatility test and thermal destruction gas chromatography mass spectrometry, and effect of DOPO on the chemical structure and composition of asphalt was explored through nuclear magnetic resonance hydrogen spectroscopy, Fourier transform infrared spectroscopy, and asphalt component testing. The results indicated that 1.0 wt% DOPO reduced the fume content of control asphalt by 1.1% from 120 ℃ − 200 ℃ and the H₂S and VOC content by 96.9% and 84.2%, respectively, at 180 ℃. Moreover, 1.0 wt% DOPO reduced the content of aliphatic hydrocarbons, hydrocarbon derivatives, aromatics, and sulfides in control asphalt fumes by 86.8%, 89.7%, 90.7%, and 93.5%, respectively, which may be attributed to electrophilic and nucleophilic reactions between DOPO and volatile substances in asphalt. Chemical structure and composition changing of DOPO-Asphalt confirmed that P-H bond in DOPO was chemically reacted with components in asphalt, generating stable aromatic hydrocarbons and resins. The results provided a novel method for inhibiting the volatilization of harmful substances in asphalt.