In blends of unsaturated polyester (UP), poly (vinyl acetate) (PVAc), and styrene, a reaction-induced phase separation occurs upon curing that is due to the crosslinking between styrene and the UP molecules. The evolution of the morphology was observed by optical microscopy on a heated stage. Light transmission was used in parallel to precisely detect the onset of phase separation and the formation of microvoids. Using Fourier transform IR spectroscopy in the same conditions, the conversions at phase separation and at microvoiding were evaluated. Phase separation occurs at a very low degree of conversion and microvoiding develops at around 60% of conversion. The final morphology of the blend was investigated by scanning electron microscopy. The relative influences of the cure temperature, the concentration in PVAc, and the molecular weight of PVAc were investigated. It was confirmed that the early stages of the reaction at high temperature determine the final morphology of the blends.