Accumulation of toxic metals generated by thermal treatment of municipal solid waste presents a serious threat to the environment. A study was carried out to investigate the kinetic law of toxic metal release from municipal solid waste during their thermal treatment. Both direct and inverse models were developed in transient conditions. The direct mathematical model of the fluid-bed reactor is based on Kunii and Levenspiel's two-phase flow model for Geldart Group B particles. The inverse model intends to predict the metal's rate of vaporization from its concentration in the outlet gas. The derived models were found to predict reasonably well the experimental observations. A method to derive the kinetic law of toxic metals release during fluidized bed thermal treatment of model waste from the global model and the experimental measurements is derived and illustrated. A first-order law was fitted for the mineral matrix, and a second-order law (simplified) was fitted for the realistic model waste. The kinetic law obtained in this way could be integrated in a global model of combustion of municipal solid waste in order to simulate the effects of operating parameters on the metal's behavior.