Detection of unreacted monomers from pre-heated resin-based dental composites (RBC) is not a well-investigated topic so far. The objectives were to determine the temperature changes during the application and polymerization, the degree of conversion (DC) and unreacted monomer elution of room temperature (RT), and pre-heated thermoviscous [VisCalor Bulk(VCB)] and high-viscosity full-body contemporary [Filtek One Bulk(FOB)] bulk-fill RBCs. The RBCs’ temperatures during the sample preparation were recorded with a K-type thermocouple. The DC at the top and bottom was measured with micro-Raman spectroscopy and the amounts of eluted BisGMA, UDMA, DDMA, and TEGDMA were assessed with High-Performance Liquid Chromatography. The temperatures of the pre-heated RBCs decreased rapidly during the manipulation phase. The temperature rise during photopolymerization reflects the bottom DCs. The differences in DC% between the top and the bottom were significant. RT VCB had a lower DC% compared to FOB. Pre-heating did not influence the DC, except on the bottom surface of FOB where a significant decrease was measured. Pre-heating significantly decreased the elution of BisGMA, UDMA, DDMA in the case of FOB, meanwhile, it had no effect on monomer release from VCB, except TEGDMA, which elution was decreased. In comparison, RBC composition had a stronger influence on DC and monomer elution, than pre-cure temperature.