Nickel-iron (Ni-Fe) alloy electrodes are synthesized using chronoamperometry. The influence of substrate type (copper, stainless steel, and nickel) and deposition potential on the structural, morphological, and electrocatalytic characteristics are systematically investigated. X-ray diffraction (XRD) analysis revealed the formation of a face-centered cubic (FCC) Ni-Fe alloy. Electrodeposition at higher potential (−1.45 V) forms well-defined nanoflakes, whereas electrodeposition at lower potential (−1.00 V) results aggregated Ni-Fe particles. The Ni-Fe alloy electrodes having well-defined nanoflakes demonstrated superior electrocatalytic performance, exhibiting a overpotential of −168 mV vs. RHE for the hydrogen evolution reaction (HER) and 236 mV vs. RHE for the oxygen evolution reaction (OER), at current density of 10 mA/cm2. The enhanced electrocatalytic activity of the nanoflakes based Ni-Fe alloy is attributed due to their larger catalytic surface area, porous morphology and higher Fe concentration. The Ni-Fe alloy electrodes displayed bifunctional electrocatalytic behavior, making them highly suitable for both HER and OER processes.