The aim of the research was to examine the effect of configuration and basic properties of membrane material on thermal protective performance against hot liquid and steam. The configuration and position of membrane material presented a significant effect on protective performance of fabric systems exposed to hot water and steam. Membrane material should be treated as outer layer to resist the penetration of hot water and steam into fabric system. A small amount of penetrating water and steam should be absorbed by the inner-layer fabric with the thicker and larger moisture regain to enhance the protective performance.