According to reports, a unique method to improve the efficiency of titanium dioxide (TiO2) dye-sensitized solar cells (DSSCs) involves inserting foreign ions into the material’s lattice structure before forming the heterostructure. The sol–gel technique has been used to produce films of TiO2, Cr–TiO2, TiO2@Cr–TiO2, and Cr–TiO2@TiO2. A small quantity of rutile phase with the anatase phase was observed in heterostructures, and XRD validated the anatase phase of pure Cr–TiO2@TiO2, which contains a large grain size (46 nm). SEM presents numerous well-formed, homogenous grains in the structure of Cr–TiO2@TiO2, providing a large surface area for dye loading in DSSCs. Among all samples, Cr–TiO2@TiO2exhibits a small band gap (Eg) (3.2 eV), and high transmittance in the visible spectrum has been observed by UV–Vis spectroscopy. The Cr–TiO2@TiO2cell demonstrates high Jsc(7.69 mA-cm−2), Voc(0.79 V), and efficiency (4.57%). The small recombination resistance, verified from EIS, is responsible for this high efficiency.