In this paper, a facile synthetic method combining the hydrothermal reaction with the liquid phase deposition (LPD) has been developed to prepare the MnO2/TiO2 composite materials from aqueous solution. The as-prepared materials were analyzed by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electronic microscopy (SEM) and transmission electronic microscopy (TEM), respectively. It could be observed that the LPD-derived anatase TiO2 nanocrystals were uniformly deposited on the alpha-MnO2 nanorods, forming a core-shell microstructure. Additionally, the cyclic voltammetry was used to evaluate the photoelectrochemical behaviors of the as-prepared materials. The results revealed that the MnO2/TiO2 composite materials exhibited larger anodic photocurrent density than that of pure MnO2 materials when the electrolyte solution (Na2SO4, 0.1 M) was saturated with CO2 gas.