To efficiently reduce and reuse fly ash from incinerators, we suggest trying a new alkaline reagent to neutralize the acid compounds in discharged gas from incinerators and reuse fly ash as the raw material in the cement industry. Normally the washing process includes a pretreatment method to remove chlorides to comply with the strict standards for cement. We examined chloride behavior in washing experiments by X-ray absorption near edge structure (XANES) and X-ray diffraction (XRD) for two kinds of fly ash: (1) fly ash collected in a bag filter with the injection of calcium hydroxide (Ca(OH)2) for acid gas removal (CaFA), and (2) fly ash collected in a bag filter with the injection of sodium bicarbonate (NaHCO3) for acid gas removal (NaFA). We found that the insoluble chlorides in both CaFA and NaFA combined calcium chloride (CaCl2), with some sodium chloride (NaCl) also possibly combined. Under some conditions, the combined CaCl2 and NaCl were released. In particular, when the liquid/solid ratio was greater than 3 or the washing frequency was doubled, less chlorine, insoluble chlorine, and CaCl2 were left in the residues of NaFA than in the residues of CaFA. As a result, it is desirable to use NaHCO3 as the alkaline reagent instead of Ca(OH)2 in the air pollution control system of incinerators for recycling fly ash as a raw material in the cement industry.