Nowadays, HCFC22 is widely used in heat pump systems in China, which should be phased out in the future. Thus, eco-friendly mixture CO2/dimethylether is proposed to replace HCFC22. Compared with pure CO2 and pure dimethylether, the mixture can reduce the heat rejection pressure, and suppress the flammability and explosivity of pure dimethylether. According to the Chinese National Standards on heat pump water heater and space heating system, performances of the subcritical heat pump system are discussed and compared with those of the HCFC22 system. It can be concluded that CO2 /dimethylether mixture works efficiently as a refrigerant for heat pumps with a large heat-sink temperature rise. When mass fraction of dimethylether is increased, the heat rejection pressure is reduced. Under the nominal working condition, there is an optimal mixture mass fraction of 28/72 of CO2/dimethylether for water heater application under conventional condensation pressure, 3/97 for space heating application. For water heater application, both the heating coefficient of performance and volumetric heating capacity increase by 17.90% and 2.74%, respectively, compared with those of HCFC22 systems. For space heating application, the heating coefficient of performance increases by 8.44% while volumetric heating capacity decreases by 34.76%, compared with those of HCFC22 systems. As the superheat degree increases, both the heating coefficient of performance and volumetric heating capacity tend to decrease.