The vaporization mechanisms of water-insoluble Cs in raw ash and Cs-doped ash during thermal treatment with CaCl addition was systematically examined in a lab-scale electrical heating furnace over a temperature range of 500-1500 °C. The results indicate that the water-insoluble Cs in the ash was associated with aluminosilicate as pollucite. Addition of 10% CaCl caused the maximum vaporization ratio of Cs in the raw ash to reach approximately 80% at temperatures higher than 1200 °C, whereas approximately 95% of Cs was vaporized at temperatures higher than 1300 °C when 30% CaCl was added. The formation of an intermediate compound, CsCaCl, through the chemical reaction of Cs with CaCl was responsible for Cs vaporization by means of the subsequent decomposition of this intermediate upon the increase in temperature. The indirect chlorination of Cs by the gaseous chlorine released from the decomposition of CaCl was insignificant. A high CaCl content in the resulting annealed products with 30% CaCl addition delayed the decomposition of CsCaCl and thus lowered the Cs vaporization ratio compared to that with 10% CaCl addition at 900-1250 °C. Thermal treatment with CaCl addition is a proposed method to remove Cs from Cs-contaminated incineration ash.