Since the first successful synthesis of zeolite from coal fly ash (ZFA) in 1985, the preparation and application of ZFA has been intensively investigated to recycle the solid waste. However, problems arising from the waste alkaline solution have rarely been addressed to date. This study initiated a novel method to synthesize ZFA/Al2O3 hybrid material by introducing a reaction step involving the neutralization of the waste alkaline solution with soluble Al salts into the traditional ZFA synthesis route. When compared with ZFA, ZFA/Al2O3 was found to have a significantly higher CEC. The increases of the BET surface area and phosphate-immobilization capacity were even more dramatic, with the former increasing by 2-4 times and the latter increasing by 2-3 times. The hybrid material had a significantly lower alkalinity than ZFA. The results also showed that the effluent from the production of the hybrid material could be much more environmentally friendly.