The purpose of the study was the investigation of the polymerization of a preheated composite resin beneath lithium disilicate. First, lithium disilicate discs in two shades (HT A2 and HT A4) and three different thicknesses (2, 4, and 6 mm) were bonded on dentine with preheated composite resin that was photo-polymerized for 20 s. The composite resin microhardness, the double bond conversion (DC) and their correlation were estimated. Second, standardized occlusal veneers of two shades and two different thicknesses (4 and 6 mm) were bonded with preheated composite resin and photopolymerized for 60 or 270 s. A microhardness line profiling was performed on the cross-section of each specimen and the correspondence DC was calculated. Shade and thickness of lithium disilicate were found to have a significant impact on micro-hardness and DC of the composite resin. Beneath standardized occlusal veneers DC can reach clinically acceptable level if photopolymerization duration is extended properly.