The coupling effects of humidity-heat on the thermal protective performance of protective clothing play an important role during the fire fighting process. The thermal stability, heat release, and thermal protective performance of protective clothing were investigated under the coupling effects of humidity-heat condition. The cone calorimeter and the thermogravimetric analysis (hereinafter referred to as TGA) were adopted to investigate the thermal stability and heat release characteristics of protective clothing. The thermal protective performance tester and heat flux meter 8 (hereinafter referred to as HFM-8) multichannel heat flow meter were adopted to simulate the multiple effects of internal sweating, external water spray and high thermal radiation. As for the thermal protective performance experiment (hereinafter referred to as TPP) results, it is found that the proper moisture content can significantly enhance the thermal protective performance, but the performance is seriously degraded after soaking, which is due to the improved thermal conductivity. The mechanism of microscopic changes of protective clothing were also investigated by hot-stage polarizing microscope and scanning electron microscope. The results of this experiment have important practical guiding significance for the safety protection of firefighters during the fire extinguishing processes.