The fire resistance of construction materials is an essential part of safety requirements in the construction industry. In this work, experimental investigations were conducted to understand the thermal behaviour, spalling, transfer characteristics, strength, and microstructures of self-cured high-strength plain (HSGC) and steel-fibre-reinforced geopolymer concrete (S–HSGC) under severe fire scenarios with peak temperatures of 275, 560, and 825 °C; the peak was maintained for a period of 120 min after reaching it. Forty-eight standard cylindrical specimens for each mixture were prepared to test and analyse their time–heat response, gradients, visual appearance, spalling, density change, water absorption, and compressive strength before and after fire exposure. Additionally, Scanning Electron Microscopy (SEM) along with Energy Dispersive X-ray Analysis (EDX) were utilised to analyse the internal structures and phase transformations. The thermal analysis showed that no cases of explosive spalling were recorded during sample exposure to various fires, while the used hook-end steel fibres had an influence on the considered test variables. The sample cores almost reached the target heat, and the thermal saturation degree at the peak ranged from 55 to 97%. The experimental findings also revealed slight surface cracking after exposure to 560 °C fires, while the surface cracking was more obvious for specimens exposed to 825 °C. Moreover, the residual compressive strength of the S–HSGC at various fires was noticeably 10.20% higher than that of the HSGC. Also, state-of-the-art research data were used to discuss the prediction model’s performance. The SEM and EDX results showed that the self-cured geopolymerization process was effective and successful in producing gels, in addition to the significant phase transformations in microstructures at different fires. This study presented sophisticated data on the behaviour of HSGC and S–HSGC exposed to fires up to 825 °C.