This chapter presents a comparative analysis of human thermal comfort and energy efficiency achieved using traditional and alternative building envelopes. In this study, an alternative envelope system, which is scientifically and environmentally sustainable, is considered. It primarily consists of outside rendered walls with polystyrene, reinforced concrete and plasterboard inside to measure the thermal comfortability index and energy efficiency within the building environment. The results are then compared with the current brick veneer building thermal comfort index and energy performance. A parametric analysis is presented highlighting the impact of traditional and alternative envelopes on thermal comfortability and energy efficiency of buildings in a subtropical climate in Australia. The results found that the new building envelope reduces the average annual cooling energy consumption by about 11% compared to that of the current building envelope with adequate thermal comfort of the occupant.