Urban pavement runoff has become an important pollution source endangering the quality of urban water. This paper analyzed the characteristics of particle size distribution of road-deposited sediment (RDS). The variation of pollutants with RDS content is presented. Based on continuous sampling of runoff, the variation between pollutant concentration and rainfall characteristics is revealed. The results show that each particle group shares similar content except for the group smaller than 0.075 mm. However, the smaller particles have a stronger ability to adsorb heavy metals (Zn, Pb, Cu), and a weaker ability to adsorb chemical oxygen demand (COD). The concentrations of different pollutants have different relationships with rainfall and runoff time. The concentration of suspended solids (SS) decreases steadily with runoff time, while the concentration of heavy metals increases first and then decreases. The first 30 minutes of runoff is the best time to treat heavy metals and SS. The five-day biochemical oxygen demand (BOD5) and total petroleum hydrocarbons (TPHs) concentration are mainly affected by rainfall intensity. The result presented in this paper may provide a useful reference for the treatment of pavement runoff pollution.