The Na-P1-type zeolite having a high cation-exchange capacity (CEC) was obtained using the waste coal fly ash from thermal power stations and a 2M NaOH solution at 100°C. The Na-P1-type zeolite was formed with the reaction time of 6 h at 100°C, and its CEC value increased with an increase in the reaction time. The addition of a suitable amount of NaAlO2 to the fly ash was also effective for improving the CEC value. A new composite material consisting of the Na-P1-type zeolite and magnetite was synthesized from the fly ash and iron chlorides because the magnetic collection was possible using this composite material after radioactive Cs+ ion adsorption. The existence of nanosized magnetites in the polycrystalline zeolite (several micrometers) was confirmed by TEM observations. The CEC and magnetic property of these composite materials were characterized.