Posttreatment of titanium oxide (TiO 2 ) using lithium (Li) and cobalt (Co) precursors is widely adopted to modify the charge quenching property in perovskite solar cells (PSCs); however, the fundamental understanding of the effect of the modification layer on the material itself and, consequently, the photovoltaic performance stability is not complete. In this work, in situ X-ray diffraction measurements show that the Li and Co ions can diffuse into TiO 2 and consequently accelerate the rutile phase transformation. X-ray photoelectron spectroscopy results reveal the appearance of a Ti 3+ feature in both the Li-and Co-treated samples, suggesting that the treatment ions are partially located at the subsurface/surface of the spin-cast TiO 2 layer. The Li-treated TiO 2 exhibits greatly upshifted conduction band edges, which benefits charge extraction properties and improves the average device parameters in a complete PSC. To complement the experiments, density functional theory calculations are performed. While Li treatment initially results in enhanced electronic properties, Li-treated TiO 2 tends to have more surface vacancies over time and is more susceptible to adsorption and accumulation of iodide ions compared to the Co-treated sample, which is experimentally supported by surface photovoltage spectroscopy and timeresolved photoluminescence results.