A novel process for preparation of micrometer-scale functional materials without organic templates has been demonstrated. Titania spheroid with a tailored core-shell structure and high ordered mesoposity has been manipulated in the ethanol hydrothermal system containing ammonia sulfate as a dispersant. Titania spheroid with a mean diameter of 3.6 μm and a high specific surface area of 266 m 2/g has been synthesized by precipitating titanium tetrachloride with ammonia gas released from hydrolysis of urea at a high temperature. A special core-shell structure with a 100 nm thin shell and a 300 nm spacing strip interiors has been characterized by SEM & TEM. The catalytic performance of the titania spheoid supported WO 3 catalyst for the selective oxidation of cyclopentene(CPE) to glutaraldehyde(GA) has been investigated. The WO 3/TiO 2 spheroid catalyst displays an exciting prospect for good selectivity(72.9%) toward GA and a high GA yield(about 70%) for the titled reaction using aqueous H 2O 2 as the oxidant.