The application of organometallic materials as anodes in fuel cell devices has experienced a notable increase in recent years. However, the use of POCOP pincer complexes remains scarcely explored despite their great relevance in catalysis. Thus, in this work, the electrocatalytic activity to methanol in alkaline media of three Ni(II)-based POCOP pincer complexes—[NiCl{C6H2-4-OH-2,6-(OPiPr2)2}] (a1), [NiCl{C6H2-4-OH-2,6-(OPtBu2)2}] (a2), and [NiCl{C6H2-4-OH-2,6-(OPPh2)2}] (a3)—will be discussed. The complexes were use as modifiers of carbon paste electrodes that were evaluated using cyclic voltammetry considering diverse factors, such as the absence and presence of MeOH, diverse proportions (% w/w) of the complex in the electrode, scan rate, and different MeOH concentrations. Results indicated the presence of a redox pair Ni(II)/Ni(III) with a quasi-reversible behavior in all complexes, the anodic peak currents of which were proportional to the increase in MeOH concentrations (0.05–0.3 mM), and their oxidation potentials varied in the function of the P-substituent in the Ni(II)-POCOPs backbone. Complex a1 exhibited the best current density (429.5 mA cm2 at 0.5 mM) compared to its analogs a2 and a3. The current intensity of all electrodes displays good stability, which remains—with slight changes—up to 100 s. Moreover, a comparison of their catalytic rate constants suggested a great activity in complex a1 (0.52 × 106 cm3 mol−1 s−1) compared to its analogues, implying a great activity in the electro-oxidation of MeOH. Hence, this work opens new opportunities for the electrochemical application of POCOPs complexes for future DMFCs development.