The flexure response of novel thermoplastic (Elium®) 3D fibre-reinforced composites (FRC) was evaluated and compared with a conventional thermoset (Epolam®)-based 3D-FRC. Ten different types of sample 3D-FRC were prepared by varying fibre orientations, i.e., 0°, 30°, 45°, 60° and 90°, and resin system, i.e., thermoplastic and thermoset. The bending characteristics and failure mechanisms were determined by conducting a three-point bend test. Results elucidate that the on-axis specimens show linear response and brittle failure; in contrast, the off-axis specimens depicted highly nonlinear response and ductile failure. The thermoplastic on-axis specimen exhibited almost similar flexure strength; in comparison, the off-axis specimens show ~17% lower flexure strength compared to thermoset 3D-FRC. Thermoplastic 3D-FRC shows ~40% higher energy absorption, ~23% lower flexure modulus and ~27% higher flexure strains as compared to its thermoset counterpart.