Purpose Firefighters are exposed to high outdoor temperature and heat stress caused by metabolic activities during firefighting and should wear protective clothing to ensure their safety and health. Traditional firefighter protective suits are bulky and heavy garments with reduced thermal comfort properties since the fabric thickness and moisture barrier layers prevent heat transfer of the garment and cause additional heat stress. The aim of this study is to reduce heat stress by creating a new fabric design with silica aerogel membrane as a moisture barrier for three-layer fabric system. Design/methodology/approach Polyacrylonitrile (PAN) nanofibers were produced with three different silica aerogel contents and used for three-layered clothing system as a moisture barrier for giving desired protectiveness and thermal comfort to firefighters. Different fabric combinations were designed using two types of outer shell fabrics, two types of moisture barrier fabrics, two types of thermal barrier fabrics and PAN/silica aerogel membranes. Findings The results show that a lighter fabric system with improved wearer's mobility and thermal comfort properties (thermal resistance and moisture permeability) is achieved with the use of PAN/silica aerogel membrane as an intermediate layer compared to commercial thermal protective fabric systems. Originality/value Differently from traditional thermal protective clothing, which may not provide adequate protection in long-term heat conditions or when exposed to flash fire, a new thermal protective clothing has been developed to be used in extremely hot environments, providing desired technical and performance properties, ease to wear comfort.