In this work, we propose that retardation in vinyl acetate polymerization rate in the presence of toluene is due to degradative chain transfer. The transfer constant to toluene (C-trs) determined using the Mayo method is equal to 3.8 X 10(-3), which is remarkably similar to the value calculated from the rate data, assuming degradative chain transfer (2.7 X 10(-3)). Simulations, including chain-length-dependent termination, were carried out to compare our degradative chain transfer model with experimental results. The conversion-time profiles showed excellent agreement between experiment and simulation. Good agreement was found for the M-n data as a function of conversion. The experimental and simulation data strongly support the postulate that degradative chain transfer is the dominant kinetic mechanism. (C) 2007 Wiley Periodicals, Inc.