We report on a combined differential scanning calorimetric (DSC) and Raman scattering study of thermal polymerization of sol-gel organic-inorganic SZ2080 and SU-8 resists. In SZ2080, endothermic peak at 95°C signify drying of the resist and justifies the required pre-bake at around 100°C for 1-2 h for the best performance during femtosecond (fs-)direct laser writing. A strong exothermic peak at 140°C (under 2 K/min heating rate) completes polymerization of the resist. It is revealed that 1wt% of photoinitiators change Raman scattering intensity of SZ2080 and can contribute efficiently to heating and cross-linking of photo-polymers. In the case of SU-8, a 65°C DSC feature related to solvent evaporation was observed. The strongest changes in Raman spectrum occurs at a narrow 895 cm-1 band which is linked to polymerization. Raman scattering taken during DSC revealed spectral changes following the polymerization; an applicability of this method for monitoring photopolymerization induced by ultra-fast laser sources and feasibility of a laser-modulated calorimetry is discussed.© (2012) COPYRIGHT Society of Photo-Optical Instrumentation Engineers (SPIE). Downloading of the abstract is permitted for personal use only.