Stricter environmental regulations demand safer treatment and disposal of incinerator fly ashes. So far no sound technology or a process is available for a sustainable and ecological treatment of the waste incineration ashes, and only partial treatment is practised for temporary and short-term solutions. New processes and technology need to be developed for comprehensive utilization and detoxification of the municipal solid waste (MSW) incinerator residues. To explore the efficiency of thermal stabilisation and controlled vitrification, the thermal behaviour of electrostatic precipitator (ESP) ash was investigated under controlled conditions. The reaction stages are identified with the initial moisture removal, volatilisation, melting and slag formation. At the temperature higher than 1100 °C, the ESP ashes have a quicker weight loss, and the total weight loss reaches up to 52%, higher than the boiler ash. At 1400 °C a salt layer and a homogeneous glassy slag were formed. The effect of thermal treatment on the leaching characteristics of various elements in the ESP ash was evaluated with the availability-leaching test. The leaching values of the vitrified slag are significantly lowered than that of the original ash.