A green template-free solvothermal approach was developed to synthesize hollow microsphere TiO2-modified in situ with nickel species (Ni2+/Ni3+). Oxalic acid played a pivotal role in the formation of hollow architecture, acting as chelating agent, structure-directing reagent, and acidity-modulation reagent, while isopropyl alcohol ensured the formation of spherical structure. The microstructure and composition of the products were characterized with various techniques, and the results showed that the products exhibited not only highly crystallized anatase phase, large specific surface areas, and the mesoporous shell and hollow architecture, but also the coexistence of Ni2+/Ni3+. The unique structure and composition of the photocatalysts resulted in improved UV and visible photocatalytic activity for degradation of Rhodamine-B and 2,4-dichlorophenol. (C) 2015 Elsevier B.V. All rights reserved.