This paper describes a facile solvothermal method to synthesize TiO2 microspheres by employing ethylene glycol monomethyl ether and ethylene glycol as solvent. By analyzing the resulted supernatant after reaction, it was proved that the etherification reaction of glycol monomethyl ether and the ligand exchange between ethylene glycol and tetra-n-butyl titanate played a key role in synthesis of TiO2 microspheres. These as-obtained TiO2 microspheres exhibited high specific surface area up to 113.24 m2 g−1 and have a narrow pore size distribution (6.94 nm). When applied to the photoanode, the TiO2 microsphere-based dye-sensitized solar cells achieved a high power conversion efficiency up to 10.25%.