ABSTRACT Clarifying the spatiotemporal distribution and impact mechanism of pollution is the prerequisite for megacities to formulate relevant air pollution prevention and control measures and achieve carbon neutrality goals. Chongqing is one of the dual-core key megacities in Cheng-Yu region and as a typical mountain-city in China, environmental problems are complex and sensitive. This research aims to investigate the exceeding standard levels and spatio-temporal evolution of criteria pollutants between 2014 and 2020. The results indicated that PM10, PM2.5, CO and SO2 were decreased significantly by 45.91%, 52.86%, 38.89% and 66.67%, respectively. Conversely, the concentration of pollutant O3 present a fluctuating growth and found a “seesaw” phenomenon between it and PM. Furthermore, PM and O3 are highest in winter and summer, respectively. SO2, NO2, CO, and PM showed a “U-shaped”, and O3 showed an inverted “U-shaped” seasonal variation. PM and O3 concentrations are still far behind the WHO, 2021AQGs standards. Significant spatial heterogeneity was observed in air pollution distribution. These results are of great significance for Chongqing to achieve “double control and double reduction” of PM2.5 and O3 pollution, and formulate a regional carbon peaking roadmap under climate coordination. Besides, it can provide an important platform for exploring air pollution in typical terrain around the world and provide references for related epidemiological research. Implications: Chongqing is one of the dual-core key megacities in Cheng-Yu region and as a typical mountain city, environmental problems are complex and sensitive. Under the background of the “14th Five-Year Plan”, the construction of the “Cheng-Yu Dual-City Economic Circle” and the “Dual-Carbon” goal, this article comprehensively discussed the annual and seasonal excess levels and spatiotemporal evolution of pollutants under the multiple policy and the newest international standards (WHO,2021AQG) backgrounds from 2014 to 2020 in Chongqing. Furthermore, suggestions and measures related to the collaborative management of pollutants were discussed. Finally, limitations and recommendations were also put forward. Clarifying the spatiotemporal distribution and impact mechanism of pollution is the prerequisite for cities to formulate relevant air pollution control measures and achieve carbon neutrality goals. This study is of great significance for Chongqing to achieve “double control and double reduction” of PM2.5 and O3 pollution, study and formulate a regional carbon peaking roadmap under climate coordination and an action plan for sustained improvement of air quality. In addition, this research can advanced our understanding of air pollution in complex terrain. Furthermore, it also promote the construction of the China national strategic Cheng-Yu economic circle and build a beautiful west. Moreover, it provides scientific insights for local policymakers to guide smart urban planning, industrial layout, energy structure, and transportation planning to improve air quality throughout the Cheng-Yu region. Finally, this is also conducive to future scientific research in other regions of China, and even megacities with complex terrain in the world.