Binary and ternary cobalt-based spinel oxides have been shown to possess enhanced electrocatalytic activity and stability towards the oxygen evolution reaction (OER), however their performance is inconsistent. In this work, copper and nickel-copper substituted cobalt spinel oxides, CuxCo3-xO4 (x = 0, 0.25, 0.5, 0.75 and 1) and NixCu1-xCo2O4 (x = 0.25, 0.5, 0.75, 0.9 and 1), were prepared by the thermal decomposition method to re-examine their properties. We used several physical and chemical characterization methods to understand their behavior. The formation of spinel structure was confirmed by X-ray diffraction analysis, however, CuxCo3-xO4 remains monophasic only up to x = 0.75. CuCo2O4 was found to contain an additional CuO phase. The lattice parameters were determined as a function of the composition and found to increase with increased Cu and Ni content in the cobalt spinel lattice, which supports Cu and Ni incorporation in the spinel structure. For CuxCo3-xO4 electrodes, the lattice parameter gradually increased when cobalt is replaced by copper in the composition. NixCu1-xCo2O4 lattice parameters are higher than those of CuxCo3-xO4 but do not display a particular trend with replacement of Cu by Ni. The XPS analysis indicates the existence of various chemical species on the surface of the electrodes with a significant amount of NiO being detected on the surface of Ni-containing samples. The core-level spectra of all metal cations indicate the presence of mixed-valence states in the spinel structure. The roughness factor was determined by measuring the double layer capacitance of the electrodes using cyclic voltammetry and the data obtained was verified by performing electrochemical impedance spectroscopy (EIS) in a region of low faradaic current. The incorporation of Cu and Ni significantly increased the surface area of cobalt oxide. The current density obtained from cyclic voltammetry (CV) data is reported as a function of the geometric and the real surface areas for each sample, which revealed that Co3O4 possesses the highest current density than other Cu or Cu and Ni-containing cobalt spinel oxides towards OER when corrected for differences in surface area. However, the addition of Cu could be viewed as beneficial as it provides a lower onset potential for OER and results in a relatively high current density compared to Co3O4. NixCu1-xCo2O4 materials have a similar current density per unit geometric area, however, when corrected for real surface area these electrodes display lower catalytic activity for OER than CuxCo3-xO4 (x = 0 to 1). The presence of a significant surface NiO species may have affected the catalytic activity of Ni-containing samples. The data will be discussed in the context of variable material performance found in the literature.