The Beijing–Tianjin–Hebei (BTH) air pollution transmission channel and its surrounding areas are of importance to air pollution control in China. Based on daily data of air quality index (AQI) and air pollutants (PM2.5, PM10, SO2, NO2, CO, and O3) from 2015 to 2016, this study analyzed the spatial and temporal characteristics of air pollution and influencing factors in Henan Province, a key region of the BTH air pollution transmission channel. The result showed that non-attainment days and NAQI were slightly improved at the provincial scale during the study period, whereas that in Hebi, Puyang, and Anyang became worse. PM2.5 was the largest contributor to the air pollution in all cities based on the number of non-attainment days, but its mean frequency decreased by 21.62%, with the mean occurrence of O3 doubled. The spatial distribution of NAQI presented a spatial agglomeration pattern, with high-high agglomeration area varying from Jiaozuo, Xinxiang, and Zhengzhou to Anyang and Hebi. In addition, the NAQI was negatively correlated with sunshine duration, temperature, relative humidity, wind speed, and positively to atmospheric pressure and relative humidity in all four clusters, whereas relationships between socioeconomic factors and NAQI differed among them. These findings highlight the need to establish and adjust regional joint prevention and control of air pollution as well as suggest that it is crucially important for implementing effective strategies for O3 pollution control.