Rapid urbanization has posed numerous negative impacts on the environment, including fine particulate matter (PM2.5) pollution. However, quantitative investigations of the PM2.5 concentration trends over an urban-rural gradient at the local level are still lacking. The urban particulate matter island (UPI) effect, representing the phenomenon that high particle concentrations in urban areas are gradually attenuated to surrounding areas, was adopted and modified in this paper to study the Hangzhou Bay area from 2000 to 2015. We found the following: (1) every urban area in the Hangzhou Bay area experienced rapid expansion, especially during 2000–2005; (2) more than half of the urban areas suffered UPI problems, and these urban areas had relatively high and stable UPI intensity (UPII) values, although the UPI footprint (UPIFP) values decreased with urban expansion; and (3) urban areas could be divided into three categories: plain areas, hilly areas and the junction of plains and hills, and the probability of the UPI effect varied significantly for different categories. This paper can compensate for the lack of research on the UPI effect at the local level and provide scientific evidence for air pollution control during urban agglomeration planning.