The objective of this study is to evaluate the impact of the thickness and translucency of various computer-aided design/computer-aided manufacturing (CAD/CAM) materials on the polymerization of dual-cure resin cement in endocrown restorations. Three commercially available CAD/CAM materials—lithium disilicate glass (e.max CAD), resin composite (CERASMART), and a polymer-infiltrated ceramic network (ENAMIC)—were cut into plates with five different thicknesses (1.5, 3.5, 5.5, 7.5, and 9.5 mm) in both high-translucency (HT) and low-translucency (LT) grades. Panavia V5, a commercial dual-cure resin cement, was polymerized through each plate by light irradiation. Post-polymerization treatment was performed by aging at 37 °C for 24 h under light-shielding conditions. The degree of conversion and Vickers hardness measurements were used to characterize the polymerization of the cement. The findings revealed a significant decrease in both the degree of conversion and Vickers hardness with increasing thickness across all CAD/CAM materials. Notably, while the differences in the degree of conversion and Vickers hardness between the HT and LT grades of each material were significant immediately after photoirradiation, these differences became smaller after post-polymerization treatment. Significant differences were observed between samples with a 1.5 mm thickness (conventional crowns) and those with a 5.5 mm or greater thickness (endocrowns), even after post-polymerization treatment. These results suggest that dual-cure resin cement in endocrown restorations undergoes insufficient polymerization.