This paper investigates the influence of exposure to elevated temperatures on the fracture mechanics of polymer concrete (PC). The PC was synthesised using epoxy, silica sand, crushed basalt, and nanoclay. The prepared PC was exposed to temperatures of 24, 40, 60, 80, 100, 120 and 140°C for two hours, and the residual fracture toughness and fracture energy in mode I and mode II were studied. The three-point bending test was conducted on cracked semi-circular bend specimens with a crack angle of 0° (pure mode I) and 41° (pure mode II) to determine the fracture parameters. Subjection to high temperatures significantly increased the fracture toughness and fracture energy of the PC. The maximum fracture toughness and fracture energy were obtained after exposure to temperatures of 120°C and 140°C, respectively. Scanning electron microscopy was used to investigate the fracture surface of the PC. The type of fracture (brittle or ductile) of the PC before and after exposure to the target temperatures was evaluated. The mathematical relationships between modes I and II critical stress intensity factor (KIc and KIIc), as well as modes I and II fracture energy (GIf and GIIf) after exposure to high temperatures, were also determined.