The photo-curing behavior of reactive blends of dipentaerythritol penta/hexaacrylate (DPHA) with an acrylated hyperbranched polyester and an acrylated hyperbranched polyether was investigated by means of photo differential scanning calorimetry. The chemical conversion data was analyzed using an autocatalytic model with close attention paid to the influence of composition, UV intensity, and vitrification. The autocatalytic model was found to be relevant to describe autoacceleration and diffusion controlled reaction stages, as long as the polymers were not vitrified. It was shown that the reaction order and the autocatalytic exponent were independent of UV intensity, whereas the rate constant showed strong intensity dependence, and the maximal conversion showed weak intensity dependence. A criterion for vitrification onset was proposed as the occurrence of a third stage in the conversion process. The ultimate conversion was found to be 0.16 higher than the conversion at vitrification for all investigated multifunctional acrylates independent of composition and UV intensity. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2366-2376, 2007