Except for providing thermal protection, thermal protective clothing (TPC) may also impose thermal hazards on human skin due to the discharge of energy storage. The dual thermal protective/thermal hazardous performance of TPC is rather complicated when TPC gets wet from internal and external sources and especially when it is exposed to conditions of pressurized hot steam. In this study, several indices were used to quantitatively investigate the influences of moisture location, moisture content within TPC, and their combined effect on the energy storage caused dual performance of TPC under exposure to steam. Results showed that both the increasing of external and internal moisture could decrease heat absorption of the skin and increase burn injury time under steam exposure through heat storage, but the positive effect of the external moisture amount was more obvious. The external moisture amount had no significant effect on heat discharge from TPC to the skin, whereas the internal moisture amount increased heat discharge. Empirical models were successfully established to predict the energy absorption of human skin and the burn injury time. Research outcomes of this study will contribute to thoroughly understanding the impact of moisture on dual performance under steam exposure and provide new insights into the development of functional textile materials.