A series including single and mixed Ni-Co aluminates was obtained using the precursor method, with malic acid as a ligand. The malate precursors (polynuclear coordination compounds) were isolated and characterized by Fourier Transform Infrared (FTIR), Ultraviolet/Visible/Near Infrared (UV–Vis–NIR) spectroscopy, and thermal analysis. The UV–Vis–NIR spectra of the synthesized complex compounds highlighted the presence of Co2+ and Ni2+ in an octahedral environment. The thermal decomposition of these precursors led to Co1−xNixAl2O4 (x = 0, 0.1, 0.25, 0.5, 0.75, 0.9, and 1) spinels. The effect of Ni2+ substitution on the structure, morphology, and optical properties of the obtained oxides was studied with the help of different characterization tools. XRD, FTIR, and Raman spectra evidenced the formation of the spinel phase. The size of the crystallites and the agglomeration degree of the particles decrease when the nickel content increases. The band gap (BG) value is not significantly influenced by the Ni substitution. The fluorescence spectra recorded for all samples show a similar pattern, but different intensities of the emission bands.