The workers of the oil and gas industry, cooks and chefs, defense personnel, firefighters, and the workers working in the boilers need to wear protective clothes to save their lives in various hazardous environments. This study addresses different thermal environments, i.e., radiant exposure, the flash of fire, etc., to design the turnout gears. The influence of various parameters of the fabric, i.e., weft, warp, moisture content at the initial stage in the material, the thickness of fabric, sequences of varying fabric layers, etc., on the shielding performance of the fabric is thoroughly elaborated. Mass transfer phenomena and their effects on the protective fiber’s protective performance are discussed in the present study. Some recent advancements in the field of Firefighter Protective Clothing (FFPC), i.e., Shape Memory Alloy (SMA) and smart coating, are elucidated in the present study to enhance protective performance. Different methods to calculate thermal damage, an influential factor of clothing performance, are well explained in the present analysis. The leading purposes of the present paper are to contribute a better understanding of heat and moisture effects on FFPC to improve safety and alleviate the risk of thermal damage. This paper also provides a thorough review of heat exposure, phase change materials, and the potential of the SMA to minimize heat transfer through FFPC.