The enduring effort toward stabilizing and improving the efficiency of dye-sensitized solar cells (DSSCs) has stirred the solar research community to follow innovative approaches. Current research centered on electrode materials design, which improves photoanodes' light-harvesting efficiency (LHE). Metal–Organic Frameworks (MOFs) are a new family of materials that can be used as competent materials due to their desirable qualities, including high porosity, flexible synthesis methodology, high thermal and chemical stability, and good light-harvesting capabilities. MOF-derived porous photoanodes can effectively adsorb dye molecules and improve LHE, resulting in high power conversion efficiency (PCE). Doping is a prospective methodology to tune the bandgap and broaden spectral absorption. Hence, a novel and cost-effective synthesis of high surface area transition metal (TM) doped TiO₂ nanocrystals (NCs) via the metal–organic framework route for DSSCs is reported here. Among the TM dopants (i.e., Mn, Fe, Ni), a remarkable PCE of 7.03% was obtained for nickel-doped samples with increased Jsc (14.66 mA/cm²) due to the bandgap narrowing and porous morphology of TiO₂. The findings were further confirmed using electrochemical impedance spectroscopy (EIS) and dye-desorption experiments. The present study expedites a promising way to enhance the LHE for many innovative optoelectronic devices.