Nanowire-based SnO2/Zn2SnO4 hollow microspheres are synthesized using a facile one-pot method for solar energy conversion and environment cleaning. The micrometer-sized hollow spheres possess a hierarchical structure with the shell consisting of nanowires. With the hybrid SnO2/Zn2SnO4 microspheres as photoanodes, the dye-sensitized solar cells (DSSCs) with an overall 4.72% photoconversion efficiency is obtained, nearly 240% improvement over the DSSCs that uses nanorod-based hierarchical SnO2 microspheres. The hybrid microspheres are also determined to be high-performance photocatalyst with a better recyclability for the photodegradation of dyes under simulated sunlight irradiation. These improvements of solar energy utilization are ascribed to the formation of the heterojunctions between SnO2 and Zn2SnO4 to enhance electron transport and charge-separation efficiencies. (C) 2014 Elsevier B.V. All rights reserved.