The reduction in chlorofluorocarbon (CFC) and hydrochlorofluorocarbon (HCFC) production and the scheduled phase-out of these ozone-depleting refrigerants require the development and determination of environmentally safe refrigerants for use in heat pumps, water chillers, air conditioners, and refrigerators. This paper presents a performance evaluation of a generic heat pump with two azeotropic refrigerant mixtures of HFC-134a (1,1,1,2-tetrafluoroethane) with R-290 (propane) and R-600a (isobutane); R-290/134a (45/55 by mass percentage) and R-134a/600a (80/20 by mass percentage). The performance characteristics of the azeotropes were compared with pure CFC-12, HFC-134a, HCFC-22, and R-290 at the high temperature cooling and heating conditions including those using liquid-line/suction-line heat exchange. The coefficient of performance of R-290/134a is lower than that of HCFC-22 and R-290, and R-134a/600a shows higher coefficient of performance than CFC-12 and HFC-134a. The capacity for R-290/134a is higher than that for HCFC-22 and R-290, and R-134a/600a exhibits higher system capacity than CFC-12 and HFC-134a. Experimental results show that the discharge temperatures of the studied azeotropic mixtures are lower than those of the pure refrigerants, CFC-12 and HCFC-22.