Metal vaporization experiments were carried out in an atmospheric fluidized bed to study the influence of operating conditions on the extent of heavy metal (HM) release in fumes from municipal solid waste incinerators. Modelwastes spiked with compounds of Pb, Cd, and Zn were used. The parameters studied were temperature, treatment duration, matrix of the model waste (mineral and organic), HM initial speciation, and gas composition (N2, air, air + HCl, gas mixture simulating the incinerators). The extent of vaporization was measured by solid sample analysis and on-line analysis of the gaseous effluent, after customization of the ICP technique for gas analysis. The results indicate the metal vaporization rate is very high initially and then slows. The results with mineral matrices give the decreasing order of volatility Cd > Pb > Zn, but in industrial incinerators Zn volatilizes slightly more than Pb. Temperature (especially for porous alumina) and mineral matrix have a strong influence on the HM vaporization, but HCl concentration and HM initial speciation do not. The gas composition and the initial metal concentration are significant parameters. The matrix influence clearly denoted the mass transfer limitations in the vaporization process from mineral matrix.