Electricity demand for room air conditioners (ACs) has been growing significantly in China in response to rapid economic development and mounting impacts of climate change. In this study, we use the bottom-up model approach to predict the penetration rate of room ACs in the residential building sector of China at the provincial level, with the consideration of the urban-rural heterogeneity. In addition, we assess co-benefits associated with enhanced energy efficiency improvement of AC systems and the adoption of low-global-warming-potential (low-GWP) refrigerants in AC systems. The results indicate that the stock of room ACs in China grows from 568 million units in 2015 to 997 million units in 2030 and 1.1 billion units in 2050. The annual electricity saving from switching to more efficient ACs using low-GWP refrigerants is estimated at almost 1000 TWh in 2050 when taking account of the full technical energy efficiency potential. This is equivalent to approximately 4% of the expected total energy consumption in the Chinese building sector in 2050 or the avoidance of 284 new coal-fired power plants of 500 MW each. The cumulative CO2eq mitigation associated with both the electricity savings and the substitution of high-GWP refrigerants makes up 2.6% of total business-as-usual CO2eq emissions in China over the period 2020 to 2050. The transition toward the uptake of low-GWP refrigerants is as vital as the energy efficiency improvement of new room ACs, which can help and accelerate the ultimate goal of building a low-carbon society in China.