Tire wear particles (TWPs) containing tire wear chemicals (TWCs) are of global concern due to their large emissions and potential toxicity. However, TWP contributions to urban fine particles are poorly understood. Here, 72 paired gas-phase and PM2.5 samples were collected in the urban air of the Pearl River Delta, China. The concentrations of 54 compounds were determined, and 28 TWCs were detected with total concentrations of 3130–317,000 pg/m3. Most p-phenylenediamines (PPDs) were unstable in solvent, likely leading to their low detection rates. The TWCs were mainly (73 ± 26%) in the gas phase. 2-OH-benzothiazole contributed 82 ± 21% of the gas-phase TWCs and benzothiazole-2-sulfonic acid contributed 74 ± 18% of the TWCs in PM2.5. Guangzhou and Foshan were “hotspots” for atmospheric TWCs. Most TWC concentrations significantly correlated with the road length nearby. More particulate TWCs were observed than model predictions, probably due to the impacts of nonexchangeable portion and sampling artifacts. Source apportionment combined with characteristic molecular markers indicated that TWPs contributed 13 ± 7% of urban PM2.5. Our study demonstrates that TWPs are important contributors to urban air pollution that could pose risks to humans. There is an urgent need to develop strategies to decrease TWP emissions, along with broader urban air quality improvement strategies.