The introduced pretreatment technology, WCCB (Washing + Calcination), was effective to reduce chlorides in fly ash by consuming relatively low energy for recycling fly ash as the raw material for cement industry. The washing conditions are: twice-washing, liquid/solid = 3, mixing speed = 150 r x min(-1), 1st mixing time = 5 min, and 2nd mixing time = 10 min. The original incinerator was used for the calcination process, 1 000 degrees C, 10% O2 and dwelling time of 1 hour were adopted. By adopting X-ray absorption near edge structure and X-ray diffraction, the behavior of chlorides was explained and NaCl, KCl and CaCl2 are the main form of chlorides existing in fly ash. The reagent used in the air pollution control system to neutralize the acid component in the discharged gas surely acted a very important role in the formation of chlorides. The insoluble chlorides in fly ash had a very similar structure as that of Friedel's salt, which was related with CaCl2.