Nickel (Ni) foam-based symmetric/asymmetric electrochemical supercapacitors benefit from a randomly 3D structured porous geometry that functions as an active material support and as a current collector. The surface composition stability and consistency of the current collector is critical for maintaining and consistency supercapacitor response, especially for various mass loading and mass coverage. Here we detail some annealing environment conditions that change the surface morphology, chemistry and electrochemical properties of Ni foam by NiO formation. Air-annealing at 400 and 800 °C and annealing also in N2 and Ar at 800 °C result in the in situ and ex situ formation of NiO on the Ni foam (NiO@Ni). Oxidation of Ni to NiO by several mechanisms in air and inert atmospheres to form a NiO coating is subsequently examined in supercapacitors, where the electrochemical conversion through Ni(OH)2 and NiOOH phases influence the charge storage process. In parallel, the grain boundary density reduction by annealing improves the electronic conductivity of the foam current collector. The majority of stored charge occurs at the oxidized Ni-electrolyte interface. The changes to the Ni metal surface that can be caused by chemical environments, heating and high temperatures that typically occur when other active materials are grown on Ni directly, should be considered in the overall response of the electrode, and this may be general for metallic current collectors and foams that can oxidize at elevated temperatures and become electrochemically active.