ZnO-TiO2 core-shell photocatalysts of a complex flower-like architecture were synthesized, using a well-controlled sol-gel coating reaction of presynthesized ZnO flower-like structures. The samples were characterized by X-ray diffraction, field emission scanning and transmission electron microscopy, energy-dispersive X-ray spectroscopy, diffuse reflectance UV-vis and attenuated total reflectance-Fourier transform infrared spectroscopy, nitrogen adsorption-desorption measurements, and photoluminescence measurements. Well-defined, core-shell flowers with a wurtzite ZnO core and anatase TiO2 shells, with variable shell thickness, were acquired by appropriately adjusting the ZnO/Ti precursor mass feed ratio in the reaction. Moreover, hollow TiO2 flowers were obtained, and they retained their morphology following the etching of the ZnO core in an acidic solution. The photocatalytic performance of the core-shell and hollow semiconductors was evaluated via the decoloration of a methylene blue dye solution under UV-vis irradiation. The core-shell flowers exhibited a higher decoloration rate, when compared with bare ZnO flowers, TiO2 particles, and hollow TiO2 flowers, and the photoactivity was dependent on the TiO2 shell thickness. This was attributed to the efficient separation of the photogenerated holes and electrons at the ZnO-TiO2 interface. Moreover, the most photoactive core-shell catalyst exhibited excellent reusability and stability for at least three photocatalytic cycles and excellent superhydrophilicity without UV irradiation, which is due to the increased roughness of the flower-like structures.