Curing kinetics are crucial for designing and optimizing the process parameters of a resin. This study examines the non-isothermal curing kinetics of acrolein-pentaerythritol (APE) resins, focusing on the impact of molecular weight (MW) and molecular weight distribution (MWD) on their cure behavior. Kinetic parameters were determined using isoconversional and combined kinetic analysis methods through microcalorimeter measurements. The findings suggest that the cure process follows the nucleation and growth models (Avrami−Erofeev equation), with an activation energy of 72.2 kJ/mol. A comparison of two APE resins with different molecular weights and molecular weight distributions reveals that higher MW components expedite the initial curing reaction but impede the main curing process, leading to extended curing durations. This study provides valuable insights into the curing kinetics of APE resin and the influence of MW and MWD, contributing to the reliable and reproducible production of composite parts.