This study has investigated the changes that might appear in post-peak flexural response. Before the flexural test, prismatic specimens were placed in a furnace chamber and exposed to elevated temperatures of 400, 600, and 800 °C. The flexural toughness test was carried out on two types of concrete: Plain ultra-high performance concrete (UHPC) and UHPC with different types of fibres (steel fibre (SF) and polypropylene fibre (PPF)) at 0.5%, 1%, 1.5%, and 2% volume fractions. During the flexural test in the macro-crack development analysis, the non-contact ARAMIS system was used to perform three-dimensional measurements of strain and displacement. The results of scanning electron microscope (SEM) observations of micro-crack development in UHPC without and with SF/PPF were also presented. The experimental results showed that in some cases, the load–deflection curve of fibre-reinforced UHPC displayed a double-peak response. The first peak signified the UHPC properties, while the second peak represented the properties of the fibres. Under flexural load, the toughness decreased as the temperature increased. Significant decrease in the load–deflection response and toughness were observed for the polypropylene fibre-reinforced UHPC when the temperature approached 800 °C. The SEM observation results showed that the thermal damage of fibre-reinforced UHPC depends on the pore pressure effect, the thermal mismatch, the decomposition of hydration products, and the formation of micro-cracks.