Metribuzin, a widely used herbicide and a frequently detected pollutant in the environment, was studied as a target compound for membrane anodic Fenton treatment (AFT), a Fenton technology with application potential for on-site treatment of pesticide wastewater. It was found that the degradation kinetics of metribuzin do not obey the AFT model, a previously developed model that fit AFT degradation kinetics of all previously investigated pesticides. The lack of fit for metribuzin data was determined to result from a weak interaction between metribuzin and the ferric ion, resulting in a significant reduction in availability of metribuzin for reaction with hydroxyl radicals during AFT, thus slowing degradation. A revised kinetic model was developed based on the original AFT model with the addition of this interaction. Results demonstrate that the new kinetic model fits metribuzin degradation data quite well at different delivery rates of Fenton reagent and at different temperatures. This weak interaction is also found to exist between ferric ion and several other triazinone/triazine herbicides during membrane AFT. The interaction intensity correlates with the electron-withdrawing/-donating property of substituents on the triazine/triazinone ring. The stronger the electron-donating ability of substituents, the stronger the interaction.