Chemorheological analyses of thermosetting polyurethane (PU) formulations containing various amounts of chain extender were carried out. In the first part of the present research, effect of chain extender content on the gel time and its dependency with temperature were investigated for PILI formulations. Gelation temperature (T-gel) and gel time (t(gel)) of reactive systems were determined using temperature sweep and time test measurements under dynamic linear viscoelastic deformations. The results of temperature sweep experiments for the samples containing various chain extender weight percents showed that the gelation temperature declined by increasing the chain extender content of PILI formulations. The analysis made on gel times determined in a wide temperature range indicated that the activation energy for the gelation process declined and 1/t(gel), as a measure of the rate of gelation process, dramatically increased with increasing chain extender concentration. In the second part of this study, calculation of viscoelastic characteristics at the gel point was performed. The results showed that the relaxation exponent (n) declined with increasing chain extender, while the fractal dimension increased. These results confirmed that the gel structures became more elastic and with a tighter structure by increasing the chain extender concentration in PU formulations. POLYM. ENG. SCI., 48:2446-2453, 2008. (C)2008 Society of Plastics Engineers