The optical frequency response and changes to the dielectric and optical parameters due to annealing temperature variation (200-500 °C) of sol-gel derived CuCoO x thin film coatings were investigated. The optical constants such as absorption coefficient, band-gaps, Urbach energy, complex refractive index, complex dielectric constants, optical dispersion parameters, and energy loss functions were determined from reflectance data analysis recorded in the ultraviolet to near-infrared (190-2200 nm) range. The absorption coefficient and the broadening of absorption edge (steepness parameter), energy band-gaps, Urbach energy, loss tangent and energy loss functions decreased with the increase in annealing temperatures. The refractive index displayed normal dispersion behaviors at higher frequency with the maximum value at a temperature of 500 °C. First-principles simulations, density functional theory (DFT+U) as implemented in the Cambridge Serial Total Energy Package (CASTEP), based on a cluster structure of Cu 0.5 Co 2.5 O 4 system, optimized the crystalline structure and calculated the electronic structure of the framework. The calculated density of states (DOS) and associated absorption coefficient and dielectric constant results reasonably support the experimental findings.