In this paper, a novel PV/e roof module was designed to act as the roof element, electricity generator and the evaporator of a heat pump system. The modules, in conjunction with a heat pump, are able to provide heat and power supply to buildings with an enhanced efficiency. Energy profiles of the PV/e modules and modules-based heat pump system were analysed and temperature distribution across the module layers was studied. It was found that the PV/e roof modules-based heat pump system can achieve significant improvement in thermal and electrical efficiencies. Variation of the system efficiencies (thermal, electrical and total) with a number of factors, i.e., top cover, PV cells, evaporation and condensation temperature of the heat pump was investigated, which led to suggestion of the optimised system configuration and operating conditions. The study indicated that the combined system should operate at 10 °C of evaporation and 60 °C of condensation temperature. Borosilicate as a top cover has better thermal performance than polycarbonate and glass; whilst the mono-crystalline photovoltaic cells are of higher electrical efficiency over the poly-crystalline and thin-films. Under a typical Nottingham (UK) operating condition, the modules would achieve 55% of thermal efficiency and 19% of electrical efficiency, while the module-based heat pump system would have an overall efficiency of above 70%. It was also addressed that the integration of the PV cells and evaporation coil into a prefabricated roof would lead to large saving in both capital and running costs over separate arrangements of PV, heat pump and roof structure.