The effects of TiCl4 post-treatment on the physicochemical properties of porous TiO2 (pTiO2) layers fabricated at 300 °C and 400 °C (denoted as pTiO2(300) and pTiO2(400), respectively) in CH3NH3PbI3 perovskite photovoltaic cells were investigated. Water contents (physisorbed water and water derived from surface hydroxyl groups) of pTiO2(300) and pTiO2(400) before and after TiCl4 post-treatment were measured by using temperature desorption spectroscopy (TDS). Moreover, structural analysis of the CH3NH3PbI3 perovskite part was performed by X-ray diffraction (XRD). In the case of pTiO2(300), the content of water was increased by the TiCl4 post-treatment due to the removal of residual organic compounds that existed before the treatment. It then caused a change in the surface activity of pTiO2(300) and enhancement of solar cell performance and photocurrent density, though suppression of CH3NH3PbI3 perovskite formation occurred. In comparison, contents of water were decreased for pTiO2(400), leading to enhancement of the conversion of PbI2 to CH3NH3PbI3 perovskite. As a result, there were significant increases in short circuit current density (Jscs) and PCEs. The results showed that TiCl4 post-treatment is an effective approach to prepare high-performance CH3NH3PbI3 perovskite solar cells without heat treatment at a very high temperature.