Accurate knowledge of the quality and environmental impact of the highway runoff in Pear River Delta, South China is required to assess this important non-point pollution source. This paper presents the quality characterization and environmental impact assessment of rainfall runoff from highways in urban and rural area of Guangzhou, the largest city of Pear River Delta over 1 year's investigation. Multiple regression and Pearson correlation analysis were used to determine influence of the rainfall characteristics on water quality and correlations among the constituents in highway runoff. The results and analysis indicates that the runoff water is nearly neutral with low biodegradability. Oil and grease (O&G), suspended solids (SS) and heavy metals are the dominant pollutants in contrast to the low level of nutrient constituents in runoff. Quality of highway runoff at rural site is better than that of at urban site for most constituents. Depth and antecedent dry period are the main rainfall factors influencing quality of highway runoff. The correlation patterns among constituents in highway runoff at urban site are consistent with their dominant phases in water. Strong correlations (r > or = 0.80) are found among chemical oxygen demand (COD), total phosphorus, Cu and Zn as well as conductivity, nitrate nitrogen and total nitrogen. O&G, COD, SS and Pb in highway runoff at urban site substantially exceed their concentrations in receiving water of Pear River. The soil directly discharged by highway runoff at rural site has contaminated seriously by heavy metals in surface layer accompanying with pH conversion from original acidic to alkaline at present.