Recent decades witnessed the increase in production and uses of HCFC-22 (chlorodifluoromethane, CHClF2) and its alternative, HFC-410A (a blend of difluoromethane and pentafluoroethane), in China in response to the booming of room air conditioners (RACs) for both domestic use and exports. HCFC-22 is an ozone-depleting substance under the Montreal Protocol, while both HCFC-22 and HFC-410A are greenhouse gases (GHGs). This study provides a most comprehensive consumption and emission inventory of refrigerants emissions (HCFC-22 and HFC-410A) from RAC sector during 1995−2014, for the first time. Our estimates show that HCFC-22 emissions increased from 0.7 Gg/yr in 1995 to 48.2 Gg/yr in 2014. The accumulative emissions contributed to global total HCFCs emissions by 4.4% (3.3%−6.1%) CFC-11-equivalent (CFC-11-eq) and 5.4% (4.1%−7.5%) CO2-equivalent (CO2-eq) during 1995−2012. If left uncontrolled, accumulative emissions of HFC-410A will be12.4 (7.1−20.2) CO2-eq Pg during 2015−2050, which can offset the global climate benefits achieved by the Montreal Protocol. The HFC-410A emissions from China’s RAC sector are estimated to be of importance to both global HFCs emissions and China’s GHG emissions. Further, we probed the emission mitigation performances of the current 2014 North American Proposal scenario and a modified more ambitious scenario. The emissions of two mitigation scenarios are only 28% and 22% of the emissions without mitigation actions, respectively. This study is the first effort to map the transition of eliminated substance HCFC-22 and its alternative HFC-410A in RAC sector. Therefore, alternative chemicals should be scrutinized with cautions before they are promoted and applied.