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Air conditioning and hot water compound system in which air-cooling heat exchanger is connected with heat recovery heat exchanger in series is studied, system fundamentals and five running modes including single refrigerating mode, single heating mode, hot water mode, refrigerating and hot water mode and heating and hot water mode are introduced, and experimental research is developed. Experimental research on operation characteristics of refrigerating capacity, heating capacity and suction and discharge temperature and pressure show that the unit operates reliably long in different operation conditions and that the variation of characteristics is within a reasonable range. Coefficient of performance of the system in refrigerating and hot water mode and in heating and hot water mode is highest with the minimal value approximately 3.2 when the temperature of water tank climbs up to 55°C, as the service efficiency of the unit is improved by recovering the condenser heat to heat hot water. The system is avoided to operate in the region of maximum power, and had better operate in the variable flow region of capillary and large air volume and small temperature difference region as much as possible.