Ten of the 25 most frequently detected hazardous contaminants at Superfund sites are chlorinated volatile organic compounds (VOCs). In this study, we explore the feasibility of using Fenton's reaction for degradation of perchloroethene. Fenton's reaction is an advanced oxidation process in which reaction of hydrogen peroxide (H2O2) with iron (Fe) generates hydroxyl (•OH) and superoxide (O2•-) radicals that can react with a wide variety of VOCs. Fenton-dependent processes can mineralize even heavily halogenated targets such as PCE and TCE. Reduction of Fe(III) to Fe(II) limits the overall rate of radical production under most circumstances. Here it was hypothesized that addition of copper to the Fenton system could increase the overall rate of •OH generation through the reduction of Fe(III) by Cu(I). At a copper-to-iron molar ratio of 2, copper addition increased the pseudo-first-order rate constant for PCE transformation by a factor of 4.3. The slopes of the Arrhenius plots for PCE consumption kinetics in copper-free and copper-amended solutions were significantly different, suggesting that copper addition changes the rate limiting step for the overall reaction. The mechanism of copper-enhanced Fenton reaction is uncertain given the complexity of the mechanism, however a plausible explanation for the kinetic enhancement observed is given. A kinetic model based on rate constants and reaction pathways reported in the literature only modestly fits the observed data and is considerably in error for certain conditions. The limitations with the literature reported values are highlighted.