Abstract Sustainable electrochemical energy generation requires cost-effective, noble-metal-free electrocatalysts for hydrogen and oxygen production in electrolyzers. This study used electrodeposition to create crystalline NiB films with different boron (B) contents—Ni-B(1.17 wt.%), Ni-B(1.06 wt.%), Ni-B(0.94 wt.%), and Ni-B(0.89 wt.%)—on FTO substrates. These films were tested as bifunctional electrocatalyst electrodes for the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) in alkaline media. The NiB films' composition and morphology were analyzed using SEM, AFM, XRD, GD-OES, and XPS. Linear sweep voltammetry assessed their electrocatalytic performance. Higher B content in the films promoted the formation of electroactive NiOOH, enhancing the OER. The Ni-B(1.17 wt.%) electrode required an overpotential of 380 mV to reach 10 mA cm⁻² for OER, while the Ni-B(1.06 wt.%) electrode required 146 mV for the same current density for HER. An alkaline water electrolyzer using Ni-B(1.17 wt.%) as the anode and Ni-B(1.06 wt.%) as the cathode achieved a current density of 10 mA cm⁻² at 1.71 V for overall water splitting. The system showed stability over 12 hours of testing. The results indicate that NiB films on FTO substrates are promising, low-cost bifunctional electrocatalysts for alkaline water electrolysis, offering an alternative to noble-metal-based electrocatalysts.