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Even though, an innovative inorganic family of geopolymer concretes are eye-catching potential building materials, it is quite essential to comprehend the fire and thermal resistance of these structural materials at a very high temperature and also when experiencing fire with a view to make certain not only the safety and security of lives and properties but also to establish them as more sustainable edifice materials for future. The experimental and field observations of degree of cracking, spalling and loss of strength within the geopolymer concretes subsequent to exposure at elevated temperature and incidences of occurrences of disastrous fires extend an indication of their resistance against such severely catastrophic conditions. The impact of heat and fire on mechanical attributes viz., mechanical-compressive strength, flexural behavior, elastic modulus; durability—thermal shrinkage; chemical stability; the impact of thermal creep on compressive strength; and microstructure properties—XRD, FTIR, NMR, SEM as well as physico-chemical modifications of geopolymer composites subsequent to their exposures at elevated temperatures is reviewed in depth. The present scientific state-of-the-art review manuscript aimed to assess the fire and thermal resistance of geopolymer concrete along with its thermo-chemistry at a towering temperature in order to introduce this novel, most modern, user and eco-benign construction materials as potentially promising, sustainable, durable, thermal and fire-resistant building materials promoting their optimal and apposite applications for construction and infrastructure industries.