The booming of China's primary aluminum industry (PAI) brought substantial emissions of hazardous air pollutants (HAPs) and greenhouse gases (GHGs). By using life cycle assessment and bottom-up method, a comprehensive emission inventory for multiple typical HAPs and GHGs from China's PAI during 1990–2021 was developed and explored for the first time. Our results show that spatial-temporal emissions trends of HAPs and GHGs from PAI in China diverse significantly. The conventional atmospheric pollutants (including SO2, NOx and particulate matter (PM)), fluoride and per fluorinated compound (PFCs) had been effectively suppressed since 2007 due to the implementation of various environmental policies; while, emissions of CO, VOCs, CH4, heavy metals and CO2 had increased at different rates unexpectedly. From the spatial distribution perspective, Henan, Shanxi, Guizhou, Guangxi and Shandong dominated the emissions of PAI in China, but with consumption expansion and environmental constrains, PAI plants start to expand to northwest and southwest areas where are richer in sufficient and cheaper power resources, thus bring significant emission increasing there, particular for conventional atmospheric pollutants in northwest and CO and VOCs in southwest China. By underlying driving forces of PAI emissions, results show that end-of-pipe control measures at various stages have played different roles to reduce emissions of the concerned species at each period, but its reduction effect diminished gradually. Future reduction should seek underlying changes in production technology and energy system. Under constrains of environmental regulation and resource endowment, promoting circular economic development for PAI would be a key strategy to reduce HAPs and GHGs emissions simultaneously in PAI.