Metal pollution of stormwater runoff can cause potential toxic impacts on the receiving water environment and human health. Effective pollution mitigation requires accurate stormwater quality modeling. Even though a significant knowledge base exists on the factors influencing metal build-up on urban roads, very limited studies have investigated how metal–particulate interaction influences metal build-up. This study quantitatively assessed the influence of particulate characteristics, together with vehicular traffic and land use, on the build-up of Zn, Cu, Pb, Cr, Ni and Cd on urban roads. The study outcomes revealed that the variability in metal build-up is highly influenced by the variability associated with metal adsorption to particulates. The percentage contribution from particulate properties influencing metal adsorption in the case of < 150 μm size road dust particles was found to be higher (Zn 44%, Cu 52%, Cr 16%, Ni 27% and Cd 45%) when compared to traffic and land use characteristics (Zn 21%, Cu 13%, Cr and Ni < 10% and Cd 34%). Similar adsorption behavior was noted for metals associated with > 150 μm size road dust particles. Among different particulate properties influencing metal adsorption, effective cation exchange capacity showed a strong positive relationship with the build-up of Cd compared to other metals, highlighting the potential role of Cd in stormwater quality as a readily available metal. The build-up of metals such as Cr and Ni are highly influenced by metal oxides of Al, Fe and Mn and clay forming minerals, indicating that Cr and Ni are relatively stable in nature.