Studies reporting the historical trends of SO2, NOx, CO, and nonmethane volatile organic compounds emissions in China using unified approaches and sources are limited. Here we established 66‐year emission trends of these four species in China. Six primary anthropogenic sources were included, and we made a series of improvements to the few existing inventories based on detailed statistical data, recently published emission factors, and technology renewal to reduce the uncertainties. National SO2, NOx, CO, and nonmethane volatile organic compounds emissions in 2015 were 27.1, 20.6, 188, and 28.4 Mt, with annual growth rates of 5.8%, 5.9%, 3.8%, and 4.6% since 1949, respectively. In recent years, fossil fuel combustion was the major contributor to SO2, NOx, and CO emissions, whereas industrial process contributed most to VOCs emissions. Our results revealed a 10% decrease in the SO2 emissions from 2005 to 2010 as a result of improvements in the flue gas desulfurization installation rate. NOx emissions stopped rising and started falling in 2011, with technology renewal and the penetration of end‐of‐pipe control measures in industrial boilers and cement production. Furthermore, we calculated future speciated VOCs emissions and ozone formation potential under alternative policy scenarios and projected to reduce emissions by 10% (compared with 2013 levels) with stringent control measures in 2020. A reactivity‐based control strategy was proposed to achieve greater ozone formation potential reductions while requiring less VOCs emissions reduction. Plain Language Summary Over past half century, the emissions of air pollutants generated through human activities in China have increased rapidly. The study of long‐term emissions trends will improve our understanding of human influence on climate change and air quality. Here we established 66‐year emission trends of four major species for the first time and evaluated the impact of government policy on emission. The central government initialed the most stringent ever action plan in China to cut emissions, for example, from 1 January 2018, China began to levy environmental protection tax, aimed at SO2, NOx, CO, VOCs, and other pollutants. Our result reveals a decrease in the SO2 and NOx emissions, consistent with satellite observation, while VOCs emissions continued to rise. The emission‐based reduction plan for VOCs have been implemented nationwide. In this study, we further proposed a reactivity‐based control strategy to improve the air quality more effectively. Key Points Historical emission trends were evaluated for SO2, NOx, CO, and volatile organic compounds (VOCs) in China since 1949 National SO2 and NOx emissions started to decline in 2007 and 2012, respectively, while VOCs emissions kept on rising A reactivity‐based control strategy was proposed to achieve greater OFP reduction with less VOCs emissions reduction