In 2017, more than 60,000 firefighters and oilfield-workers injuries and fatalities occurred while they were working under various thermal hazards such as flame, radiant heat, steam, etc., or due to their significant heat stress related discomfort. The majority of these burn injuries and fatalities results from an inadequate protection and comfort provided by firefighters’ and oilfield-workers’ fire protective polymeric textile materials used in their workwear. Hence, both the thermal protective and thermo-physiological comfort performance of fabrics used in workwear significantly contribute to limit firefighters’ and oilfield-workers’ skin burns and heat stress. Considering this, previous studies have focused on characterizing and developing empirical models to predict the protective and comfort performance based on physical properties of the fabrics. However, there are still some technical knowledge gaps in the existing literature related to this. This paper critically reviewed the literature on characterization and modeling of thermal protective and thermo-physiological comfort performance of fire protective textile fabric materials. The key issues in this field have been indicated in order to provide direction for the future research and advance this scientific field for better protection and comfort of the firefighters and oilfield-workers.