Increasing the photocurrent is one of the main objectives of the current research on aqueous photovoltaic cells, the emerging green, alternative technology in solar energy conversion devices. In such a scenario, this work deals with the thorough understanding of the electrochemical and photoelectrochemical effects of the TiCl4 treatment onto TiO2 electrodes, a well-known process for traditional dye-sensitized solar cells, and here, to our knowledge, investigated for the first time in water-based systems. From the quantitative evaluation of the photoelectrochemical parameters, it emerges that the TiCl4 treatment beneficially affects the photovoltaic parameters: it doubles the sunlight conversion efficiency values, inhibits the recombination of photogenerated electrons with oxidized redox mediator ions, and ensures stable and reproducible cell performance at the laboratory scale. (C) 2019 Elsevier Ltd. All rights reserved.