Bandgap tuning is a key approach to optimizing materials for advanced technologies, enabling the development of more efficient and specialized devices. In this study, we demonstrate the tunability of the bandgap of CuCrO2 from 2.38 to 4.37 eV via single cation-doping with Ni and Zn, and multi-cation doping with Ni-Zn and Ni-Zn-Mg. XRD analysis reveals structural changes due to lattice distortions by cationic substitution, while FESEM shows the impact of doping on particle size, surface morphology, and crystallinity. The lamellar structure observed with multi-cation doping in FESEM investigations indicates increased structural disorder and defects, causing tailing above the valence band and below the conduction band, significantly reducing the bandgap. The effect of Zn-Ni doping on the lattice is reversed with Mg2+ insertion due to p-p orbital interactions between Mg2+-O, replacing the d-p interaction in the Cr3+-O bond, as confirmed by optical studies. UV–Vis and photoluminescence analyses reveal significant shifts in bandgaps and emission spectra, with Ni doping yielding a bandgap of 3.97 eV, Zn doping 3.16 eV, Zn-Ni doping expanding it to 4.37 eV, and Zn-Ni-Mg doping reducing it to 2.38 eV. The dopants also affect emission characteristics, including band edge and deep-level emissions. This study provides valuable insights into the relationship between cationic doping and material properties, guiding the design of CuCrO2-based materials with tailored functionalities.