Road dust from coal utilization is a significant source contributing to the generation of pollutants that can affect the health of people residing within close proximity to roadways. In this study, road dust samples were collected from different directions centered around a coal-fired power plant in Huainan. Black carbon (BC), soot, char, organic carbon (OC) and total carbon (TC), as well as the delta C-13 of samples, were determined. Compared to the reference locations which were distant from the power plant, the research areas surrounding the power plant were featured by significantly higher OC/BC ratio and TC concentration. The OC/BC showed significant difference in urban vs. rural areas, and at different distances from the central power plant, which implied that the source and spread of carbonaceous species was dominantly affected by wind direction and urban/rural area differences. Surface morphology analysis showed that the road dust was mixed with spherical particles similar to fly ash. High-resolution XPS C1s spectrum revealed the existence of metal carbide, metal carbonate, and CF3 in the road dust samples. The speciation of carbon in road dusts was found correlated with sampling directions and urban functional areas. Based on the delta C-13 and OC/BC, it could be inferred that coal-related substances might be important sources of road dusts.