The paper presents a complex model of heat and mass transfer in a multi-layer protective clothing exposed to a flash fire and interacting with the human skin. The clothing was made of porous fabric layers separated by air gaps. The fabrics contained bound water in the fibres and moist air in the pores. The moist air was also present in the gaps between fabric layers or internal fabric layer and the skin. Three skin sublayers were considered. The model accounted for coupled heat transfer by conduction, thermal radiation and associated with diffusion of water vapour in the clothing layers and air gaps. Heat exchange due to phase transition of the bound water were also included in the model. Complex thermal and mass transfer conditions at internal or external boundaries between fabric layers and air gaps as well as air gap and skin were assumed. Special attention was paid to modelling of thermal radiation which was coming from the fire, penetrated through protective clothing and absorbed by the skin. For the first time non-grey properties as well as optical phenomena at internal or external boundaries between fabric layers and air gaps as well as air gap and skin were accounted for. A series of numerical simulations were carried out and the risk of heat injures was estimated.