The resistance to delamination in polymer composite depends on their constituents, manufacturing process, environmental factors, specimen geometry, and loading conditions. The manufacturing of laminated composites is usually carried out at an elevated temperature, which induces thermal stresses in composites mainly due to a mismatch in the coefficient of thermal expansion (CTE) of fiber and matrix. This work aims to investigate the effect of these process-induced stresses on mode-I interlaminar fracture toughness (GI) of Glass-Carbon-Epoxy (GCE) and Glass-Epoxy (GE) composites. These composites are prepared using a manual layup technique and cured under room temperature, followed by post-curing using different curing conditions. Double cantilever beam (DCB) specimens were used to determine GI experimentally. The slitting technique was used to estimate residual stresses (longitudinal and transverse direction of crack growth) inherited in cured composites and the impact of these stresses on GI was investigated. Delaminated surfaces of composites were examined using a scanning electron microscopy (SEM) to investigate the effect of post-curing on the mode-I failure mechanism. It was found that GI of both GE and GEC composites are sensitive to the state of residual stress in the laminas. The increase in the GI of laminates can also be attributed to an increase in matrix deformation and fiber–matrix interfacial bond with the increase in post-curing temperature.