Air pollutants have been investigated in many studies, but the variations of atmospheric pollutants and their relationship with rainwater chemistry are not well studied. In the present study, the criteria atmospheric pollutants in nine monitoring stations and rainwater chemistry were analyzed in karst Guiyang city, since the time when the Chinese Ambient Air Quality Standards (CAAQS, third revision) were published. Based on the three-year daily concentration dataset of SO2, NO2, CO, PM10 and PM2.5, although most of air pollutant concentrations were within the limit of CAAQS III-Grade II standard, the significant spatial variations and relatively heavy pollution were found in downtown Guiyang. Temporally, the average concentrations of almost all air pollutants (except for CO) decreased during three years at all stations. Ratios of PM2.5/PM10 in non- and episode days reflected the different contributions of fine and coarse particles on particulate matter in Guiyang, which was influenced by the potential meteorological factors and source variations. According to the individual air quality index (IAQI), the seasonal variations of air quality level were observed, that is, IAQI values of air pollutants were higher in winter (worst air quality) and lower in summer (best air quality) due to seasonal variations in emission sources. The unique IAQI variations were found during the Chinese Spring Festival. Air pollutant concentrations are also influenced by meteorological parameters, in particular, the rainfall amount. The air pollutants are well scoured by the rainfall process and can significantly affect rainwater chemistry, such as SO42−, NO3−, Mg2+, and Ca2+, which further alters the acidification/alkalization trend of rainwater. The equivalent ratios of rainwater SO42−/NO3− and Mg2+/Ca2+ indicated the significant contribution of fixed emission sources (e.g., coal combustion) and carbonate weathering-influenced particulate matter on rainwater chemistry. These findings provide scientific support for air pollution management and rainwater chemistry-related environmental issues.