With the rapid industrial development and urbanisation in China, nitrogen dioxide \({(\mathrm{NO}}_{2})\) pollution has become a severe environmental problem that threatens public health. Based on hourly concentration monitoring data of the six main air pollutants in mainland China, a space–time Bayesian hierarchy model was employed to analyse the spatiotemporal trends of the absolute and relative \({\mathrm{NO}}_{2}\) concentrations (i.e., the proportion of \({\mathrm{NO}}_{2}\) in the six main air pollutants: \(\mathrm{CO}\), \({\mathrm{NO}}_{2}\), \({\mathrm{PM}}_{2.5}\), \({\mathrm{PM}}_{10}\), \({\mathrm{O}}_{3}\), and \({\mathrm{SO}}_{2}\)). Both the absolute and relative \({\mathrm{NO}}_{2}\) concentrations were higher in the autumn and winter of each year during the study period. Four regions in particular—the North China Plain, the Yangtze River Delta, the Sichuan Basin, and the Pearl River Delta—experience the largest amounts of \({\mathrm{NO}}_{2}\) pollution, with a high local magnitude of more than 1.0 relative to the overall absolute and relative \({\mathrm{NO}}_{2}\) concentrations; this affects an area with a human population of 571.85 million, which is 42.47% of the total population. Central China (i.e., the Shaanxi–Shanxi–Henan region) and the Tarim Basin (northwest of Xinjiang) were heavily polluted by \({\mathrm{NO}}_{2}\) and other pollutants throughout the year, with a high local magnitude of more than 1.0 relative to the overall absolute \({\mathrm{NO}}_{2}\) concentration. The \({\mathrm{NO}}_{2}\) pollution in most of the cities in western and southern China is less serious, along with cities in the northeast. Local trends reveal that in general, cities with high \({\mathrm{NO}}_{2}\) pollution are accompanied by upward trends. Specifically, except for in the summer, there were about 86 cities showing the increasing trend, of which 66 cities are located in areas with higher absolute and relative \({\mathrm{NO}}_{2}\) concentrations. Taiyuan, for example, represents the maximal local trend, with an average annual increase of 4.39 (95% CI 1.61–7.43) \({\mu g}/{{m}}^{3}\) and 0.43 (95% CI 0.16–0.73) %, respectively, which will lead to further increases in the population exposure-risk in heavily polluted areas.