Zhundong (ZD) coal gasification/combustion fly ash is a high Na content residual product and contains a large quantity of harmful elements, including as Cl, S, and Na that must be removed and recovered. Water-soluble Na is the predominant Na form in ZD coal fly ash, accounting for 34.7-92.8% of the total Na. The main minerals of Na identified were NaCl and Na2SO4. Most of the water-soluble Na in the ZD coal fly ash can be effectively removed by water washing, the removal yields have been found to be 31-93%. Increasing the washing time, water temperature, liquid-solid ratio and acid concentration can increase the Na removal yield. For the ZD coal combustion fly ash (SEHcf) and gasification fly ash (SEHf), NaCl particles are present on the fly ash surface, most water-soluble Na was washed by water in 5 min at 30 degrees C. However, the removal of Na by water washing was inhibited by the water insoluble calcium oxides and sulfides that covered the surface of the ZD coal gasification fly ashes (TCf and SHf), Na removal required higher wash water temperatures and longer washing times. It is feasible to recover Na from ZD coal fly ash by water washing, and the recovered Na products are primarily NaCl and Na2SO4. The recovery yields of Na in the SEHcf, SEHf and TCf were 49.4%, 81.2%, and 65.4%. But the recovery yield of Na in SHf was 16.6%. SEHcf, SEHf and TCf were more suitable for recovering Na. the recovery of Na from ZD coal fly ash is economically feasible.