Nickel oxide (NiO) was synthesized using several methods and the various physical characteristics observed were correlated to differences in electrocatalytic activity, specifically relating to the oxidation of methanol in alkaline media. Room temperature NaOH-precipitated NiO showed the highest activity and stability towards methanol oxidation in hydroxide (0.005M KOH) and carbonate (0.1M Na2CO3) media of similar alkalinity. Rapid degradation of NiO electrodes was attributed to microcracking and disintegration associated with the formation of the γ-NiOOH/α-Ni(OH)2 redox couple, in addition to repeated scans through the oxygen evolution reaction region. Carbonate electrolytes also exhibited average current ranges 3–4 times higher and charge transfer resistances around 85% lower than hydroxide electrolytes. This suggests carbonate may provide a better medium in terms of higher activity and more moderate alkalinity for electrochemical reactions than hydroxide solutions.