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With the energy crisis and resource depletion nowadays, novel, highly performing, and cost-effective semiconductors are in urgent demand for efficiently harvesting solar energy for photoelectrochemical applications. Herein, this study presents low-cost anatase TiO hollow nanoparticles as prepared by a critical liquid-phase deposition (LPD) processing combined with a hydrothermal reaction and calcination processing, without involving any templates. The additional LPD processing not only makes the resulting samples more visible light responsive, but also results in hollowing the TiO nanoparticles (nanosheets vs. hollow nanoparticles). Importantly, commercial TiO powder is employed as the starting material to achieve the final synthesis of TiO hollow nanoparticles, making it scalable and cost-effective for production and applications. As a by-product, the fluoride, formed during the preparation process, is assumed to play a significant role in hollowing through chemically induced self-transformation and Ostwald ripening, in addition to enhancing the crystallinity. The beneficial structural evolution to the hollow nanoparticles enables the improvement of the photoelectrochemical performance through impressive inhibition of the recombination of the photoelectrons and holes, which is well evidenced by I and EIS (Nyquist plot), as well as by I- V curve and electron lifetime evaluations as for the assembled DSSCs with the prepared TiO hollow nanoparticles under simulated sunlight illumination (50 mW/cm). [ABSTRACT FROM AUTHOR]