The increasing demand for high-performance composites has driven the need for sustainable alternatives to conventional petroleum-based resins. This research introduces a novel glycerol-derived bio-epoxy resin and investigates the effect of catalyst concentration on its curing behaviour, network structure, and thermomechanical performance. Four catalyst concentrations were evaluated using differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), and dynamic mechanical analysis (DMA) combined with tensile, flexural, and compression testing. DSC results revealed that increasing the catalyst concentration significantly lowered the curing activation energy, shifting the exothermic peak temperature from 194.8 °C to 145.2 °C. DMA revealed that the glass transition temperature (T_g), crosslinking density, and stiffness consistently increased up to an optimal catalyst concentration, reaching a maximum T_g of 109.0 °C. Further increases in catalyst content led to slight reductions in T_g and crosslink density due to the formation of a heterogeneous network. The optimal concentration enhanced tensile and compressive strength by 32.8% and 9.3%, respectively. At excessive catalyst concentration, strength properties deteriorated despite increased material rigidity. These findings confirm the critical role of catalyst in governing polymerisation kinetics and network structure, demonstrating that an optimal catalyst percentage is essential for maximising strength and durability, making the bio-epoxy a viable, high-performance alternative for advanced composite manufacturing.