Fine particle is a crucial air pollutant in terms of its impact on ambient environment, citizens health and traffic visibility. In this study, temporal and spatial variations of PM2.5 were analyzed in Beijing, Shanghai, Guangzhou, Chengdu and Shenyang in China from June 2013 to May 2017 using hourly data collected from U.S. Embassy and consulate monitoring system. The distribution of annual, seasonal, monthly and diurnal concentration was illustrated by attainment rate, severity rate, as well as the time length. After that, coefficient of divergence (COD) was adopted to study the spatial heterogeneity among five typical megacities. Additionally, the relationship between PM2.5 and meteorology was calculated by Pearson correlation and stepwise multiple linear regression. The results show that annual PM2.5 concentrations were overall downward trends in all areas. Clear seasonal variations were identified with the slightest pollution in summer and the severest in winter. Hourly distribution was dramatically different while the average concentration during daytime was higher than night except Shanghai, and the weekends had higher pollution than the weekdays except Chengdu. Besides, monthly attainment rate displayed inverted-U distribution, oppositely, severity rate revealed U-shaped distribution. With the increasing pollution levels, the time length of PM2.5 pollution was observed continuous declining in Guangzhou, Shanghai and Beijing, but a fluctuation in other two cities. Furthermore, COD values indicated that there was obvious spatial heterogeneity between Beijing, Chengdu, Shenyang and Shanghai, Guangzhou. As for meteorology, pressure had a significantly positive impact on PM2.5 concentration, while temperature and rainfall had negative influence. These results demonstrate the pollution levels of PM2.5 in different cities at distinct time and confirm the important role of meteorological conditions in air quality, and the findings also provide forecast models of PM2.5 in five cities.