A seed-induced in-situ hydrothermal conversion technique is proposed to prepare novel hollow microspheres with zeolite/mullite composite shells from fly ash cenosphere (FAC), a solid waste with a hollow structure from coal power stations. Two groups of hollow microspheres were prepared, one with zeolite FAU/mullite composite shells and the zeolite LTA/mullite composite shells. The FAC in this study plays dual roles as both the template cores and the aluminosilicate nutrition contributor. The final products inherit the hollow spherical morphology of FAC and possess zeolite crystals and the inner porous shell of mullite. Such hollow zeolitic materials are expected to have many advantages in applications such as catalysis, adsorption, separation, and as releasing capsules.