Chromium (Cr), one of the prime hazardous trace elements in coals, may engender adverse effects on eco-environment and threaten human health during utilization of coal. Based on the samples obtained in our laboratory and published literature, the abundance and modes of occurrence of Cr in Chinese coals, and the environmental impacts associated with coal-fired power plants (CFPPs) were elucidated in this study. With a total of 1397 sets of data, the mean concentration of Cr in Chinese coals was calculated as 21.33 μg/g by the “reserve-concentration” weighted calculation method. Spatially, the average Cr contents increased gradually from North China to South China. Temporally, coals from T 3, E–N and P 2 were relatively enriched in Cr compared to the other geological time. The Cr concentration in coal varied with different coal ranks. The geological factors accounted for Cr enrichment in coals could be divided into the primary, secondary and epigenetic processes. Higher percentages of organically Cr occurred in low-rank coals, while inorganically associated Cr was mainly found in clay minerals. After coal combustion, most of Cr was enriched in solid wastes (e.g., fly ash and bottom ash). The leaching of Cr from solid wastes in the rainy season (especially acid rain) needs to be a concern for CFPPs. It was estimated that the atmospheric emission of Cr from CFPPs increased annually from 2015 to 2019 and reached approximately 159 tons in 2019.