CSA/GFRC is an advanced composite material possessed with great ductility and durability. However, its bending performance and fibre condition, as well as intrinsic microstructural changes, under elevated temperature have not been understood so far. XRD was applied in this study to investigate the hydration mechanism of CSA cement under 50°C, 70°C, and 80°C. Bending performance was carried out to test the toughness of CSA/GFRC. SEM was applied to observe the underlying microstructural changes of CSA/GFRC under different curing regimes. It was found out that there was a gradual degradation of both ultimate tensile strength and ultimate strain of CSA/GFRC with elevated curing temperature and curing age, but glass fibre still shows considerable ability to carry stress alone by bridging cracks. Microstructural studies showed that, at accelerated temperatures of 50°C and 70°C, the space between fibres remained empty in general only with some hydration products adhering to the fibre surface occasionally. At a higher accelerated curing temperature of 80°C, densification of the interfilamentary spaces by larger and clustered hydration products can be observed at longer curing ages, causing the fibres to lose parts of the flexibility. Therefore, it can be concluded that densification of interfilamentary spaces may have a greater role to play in the strength degradation of CSA/GFRC than mechanisms associated with fibre weakening caused by chemical corrosion.