The effects of isothermal temperature on the curing extent, gel time, dynamic rheological behaviors, and mechanical properties of vinyl ester resins (VERs) were systematically studied. Although, the curing extent was observed increase with increasing the operating temperature, the study of residual heat of cured VERs indicated that the final curing extent depended on the postcuring process. The values of shear storage and loss modulii at gel point were observed to decrease with increasing both the isothermal temperature and heating rate, which were associated with the formation of microgels during the gelation process. With increasing isothermal temperature and heating rate, the microgel did not have enough time to grow well, causing a reduced shear storage and loss modulii at the gel time. The storage and loss modulii of the cured VERs were also studied and shown that with temperature increased to the glass transition, both modulii were first decreased and then increased. © 2013 American Institute of Chemical Engineers AIChE J, 60: 266–274, 2014