摘要： The novel urchin-like and yolk-shell titania microspheres (henceforth called UYTMs) with nanowires/microspheres hierarchical structures were successfully synthesized by a synthetic sol-gel and hydrothermal method without using any template. Uniform TiO2 microspheres were firstly prepared by the sol-gel method, and the great monodispersed properties was delicately regulated by using the surfactant of KCl, aniline and a proper amount of water. The urchin-like yolk-shell morphology was further achieved by a NaOH-assisted hydrothermal process, and the diameter and shell thickness of the UYTMs were highly controlled by the concentration of NaOH. The detailed morphology, chemical composition and crystallinity of the UYTMs were systematically characterized by several techniques, and the underlying formation mechanisms was attentively discussed as well. The photodegradation of methylthionine chloride experiments indicated the UYTMs showed much better photocatalytic activity than that of commercial P25. This is mainly because the UYTMs exhibited much more reactive sites, higher adsorption ability and tuned optical absorption behavior owing to their large specific surface area, hierarchical structures and the special hollow yolk-shell structure.