China is suffering severe ambient air pollution in recent decades and particulate matter (PM) has become the major pollutant, especially for PM2.5 and PM10, which have highly raised scholars and policy-makers’ attention in last few years. The existing research has focused on the characteristics of PM2.5 and PM10, respectively, or analyzed the correlation between the two pollutants, while the ratio of PM2.5 to PM10 has been taken less consideration. In this study, daily mean PM2.5 and PM10 mass concentrations in 31 provincial capitals from 2014 to 2016 were used to present the temporal variations and spatial distribution of PM2.5/PM10 ratios among eight economic regions. And then, statistical method and correlation analysis were adopted to investigate the relationship between the ratios and AQI, the rate of change on the ratios, and the impact of meteorological parameters on the ratios. The results indicated that PM2.5/PM10 ratios showed an increasing trend from northwest to southeast due to different economic development and industrial types. The highest values were observed in winter among all regions, and the ratios on weekends were higher than that of on weekdays in most of the regions. Besides, domestic heating in northern China had a significant contribution to the ratios. Moreover, ratios had less changes, and the rate of change was stable in summer. As for air quality, the higher the ratio, the larger the possibility of high AQI so that the air pollution will be more severe. In terms of meteorological factors, the results demonstrated that relative humidity, precipitation, and pressure were the most important factors and had significantly positive impacts, while sunshine duration, temperature, and wind speed had negative effects on the ratios. The findings could identify the pollution sources among PM10 and be helpful for making regulation locally to reduce emission which considers anthropogenic sources and meteorological diffusion simultaneously.