A hot water and steam tester was used to examine thermal protective performance of waterproof and breathable fabric against hot water and steam hazards. Time to cause skin burn and thermal energy absorbed by skin during exposure and cooling phases was employed to characterize the effect of configuration, placing order and properties of waterproof and breathable fabric on the thermal protective performance. The difference of thermal protective performance due to hot water and steam hazards was discussed. The result showed that the configuration of waterproof and breathable fabric presented a significant effect on the thermal protective performance of single- and double-layer fabric system, while the difference between different configurations in steam hazard was greater than that in hot water hazard. The waterproof and breathable fabric as outer layer provided better protection than that as inner layer. Increasing thickness and moisture regain improved the thermal protective performance of fabric system. Additionally, the thermal energy absorbed by skin during the cooling phase was affected by configuration, thickness and moisture regain of fabric. The findings will provide technical data to improve performance of thermal protective clothing in hot water and steam hazards.