In this report, Zn2SnO4 microspheres with controllable shell numbers have been synthesized for the first time via a sol-gelroute followed by a hydrothermal process, and have been used as electrodes for assembling dye-sensitized solar cells. It is found that the photovoltaic properties of cells is influenced by shell number and the best efficiency of 5.04% can be achieved for the cell composed of microsphere with a double-shell structure. This result might be contributed to the fact that the electrode composed of double-shell microspheres could increase dye adsorption amount, charge collection efficiency, and light scattering ability and suppress charge recombination.