Toughened epoxy systems have found increasing applications in automotive, aerospace, and electronic packaging industries. The present article reported work done for elucidation of gelation and vitrification for various epoxy systems and their blends with dendritic hyperbranched polymers (HBPs) having epoxy and hydroxyl functionality. Gel time was found to increase with increasing functionality from diglycidyl ether of bisphenol A (DGEBA) to tetraglycidyl diaminodiphenyl methane (TGDDM). The vitrification point was clearly identified from rheological experiments for triglycidyl p-amino phenol (TGAP) and TGDDM. In the case of DGEBA a clear display of vitrification was not observed. TGDDM underwent vitrification sooner than did TGAP. Hydroxyl-functionalized HBP reduced the gel time of the blends because of the accelerating effect of -OH groups to the epoxy curing reaction. (C) 2004 Wiley Periodicals, Inc.