The vaporization phenomena of cesium (Cs) from molten slag have been investigated in a plasma melting process for simulated radioactive waste materials. A direct current transfer-type plasma with a maximum output of 50 kW was used to melt carbon steel and granular oxide mixtures (Fe2O3, Al2O3, SiO2, CaO, and MgO) containing nonradioactive cesium nitrate, to measure Cs vaporization. These materials are the main components of low-level miscellaneous solid wastes. The vaporization rate of Cs from the molten slag during the plasma melting was observed and was compared with the vaporization rate obtained in an electric resistance furnace. The apparent vaporization rate of Cs was found to follow the first-order rate equation with respect to the molten slag's Cs content, and its rate constant values varied (3.5 to 21.0) × 10-6 m/s varying with the chemical composition of the miscellaneous solid wastes. These rate constants were about one order larger than those obtained in the electric resistant furnace and also the diffusion coefficients of basic elements in the molten slag. These results suggest that the vaporization rate of Cs is controlled by the vaporization step from the free molten slag furnace to the gas phase and depends predominantly on the thermodynamic properties of the molten slag.