The fly ash–ground granulated blast-furnace slag-based geopolymer (FSG) represents a groundbreaking material, offering a sustainable and environmentally friendly alternative to conventional construction materials. This paper presents a systematic experimental study on FSG reinforced with carbon fibre (CF, 0%–1.0%) and nano-silica (NS, 1%–3%) at high temperatures (20, 200, 400, 600, 800, and 900 °C). Various tests concerning appearance, residual strength, uniaxial tension, XRD, FTIR, TGA, SEM, and air-void characteristics were conducted to analyse thermal effects. The findings show that as temperature increases, the colour of the geopolymer transitions from dark grey to yellow grey. Enhanced geopolymerisation during thermal solidification from 20 to 400 °C significantly increases the compressive, flexural, and tensile strengths of the geopolymer. The addition of CF and NS improves the residual strength of geopolymers at high temperatures, with optimal concentrations found to be 0.6% for CF and 2% for NS. CF maintains its bridging effect at high temperatures, enhancing fibre–matrix bonding, while NS promotes the formation of additional hydration products on CF surfaces, thereby strengthening the material further. After exposure to 800 °C, despite a weakening of the fibre–matrix interface, the modified geopolymers (FSGC0.6 and FSGC0.6N2) exhibit finer air bubble chord lengths and superior air-void characteristics than the control group. This supports the theory that the synergistic action of CF and NS not only enhances geopolymerisation but also fills pores, thus limiting crack propagation and densifying the pore structure.
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