This communication presents results from dynamic mechanical analysis and measurement of charge-recombination luminescence showing that the vitrification process during isothermal cure of an acrylate resin appears to proceed in two steps. Glass formation, as determined by charge-recombination luminescence, is found to occur much before macroscopical gelation and vitrification are detected in dynamic mechanical analysis. This suggests the presence of a micro-vitrification transition in addition to the analogous micro-gelation process which has been reported in diacrylate polymerisations.