Heat pipes and two‐phase thermosyphon systems are passive heat transfer systems that employ a two‐phase cycle of a working fluid within a completely sealed system. Consequently, heat exchangers based on heat pipes have low thermal resistance and high effective thermal conductivity, which can reach up to the order of (105 W/(m K)). In energy recovery systems where the two streams should be unmixed, such as airconditioning systems of biological laboratories and operating rooms in hospitals, heat pipe heat exchangers (HPHEs) are recommended. In this study, an experimental and theoretical study was carried out on the thermal performance of an air‐to‐air HPHE filled with two refrigerants as working fluids, R22 and R407c. The heat pipe heat exchanger used was composed of two rows of copper heat pipes in a staggered manner, with 11 pipes per row. Tests were conducted at different airflow rates of 0.14, 0.18, and 0.22m3/h, evaporator inlet‐air temperatures of 40, 44, and 50°C, filling ratios of 45%, 70%, and 100%, and ratios of heat capacity rate of the evaporator to condenser sections (Ce/Cc) of 1 and 1.5. For HPHE's steady‐state operation, a mathematical model for heat‐transfer performance was set and solved using MATLAB. Results illustrated that the heat transfer rate was in direct proportion with the evaporator inlet‐air temperature and flow rate. The highest HPHE's effectiveness was obtained at a 100% filling ratio and (Ce/Cc) of 1.5. The predicted and experimental values of condenser outletair temperature were in good agreement, with a maximum difference of 3%. HPHE's effectiveness was found to increase with the increase in evaporator inletair temperature and number of transfer units (NTU) and with the decrease in airflow rate, up to 33% and 20% for refrigerants R22 and R407c, respectively. Refrigerant R22 was the superior of the two refrigerants investigated.