Solvothermal synthesis is considered a novel method of preparing the photoanode in dye-sensitized solar cells (DSSCs), which can directly synthesize material with good crystallinity at low temperatures without thermal treatment. However, how thermal treatment influences the properties of the materials synthesized by this method is still unclear, especial at the microscopic level. In this study, we applied TiO2 nanorod arrays prepared by the solvothermal method to DSSCs. X-ray Diffraction (XRD) and Raman results indicate that the crystal structure of TiO2 nanorods did not change after thermal treatment. However, the photovoltaic performance improved by 39%. Detailed analysis of high-resolution transmission electron microscopy (HRTEM) results demonstrate that a surface reconfiguration occurred, shifting one thin amorphous TiO2 layer to tiny crystallite spheres. The X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR) measurements further confirm this morphology change, and the surface states also become more suitable for dye absorption, which leads to a significant improvement in efficiency. Moreover, good electrical transport is observed due to the low concentration of surface defects. Therefore, we believe the performance improvement comes from crystalline surface and surface chemical bonding improvements. Our results could be useful in photoelectrical applications of the solvothermal synthesis method. Crown Copyright (C) 2014 Published by Elsevier B.V. All rights reserved.