Electrocatalytic water splitting is a promising method for high-efficiency hydrogen (H₂) production, providing a clean and sustainable alternative to fossil fuels. However, the development of efficient, cost-effective, and durable nonprecious metal electrocatalysts for both the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) remains a significant challenge. In this study, a novel electrocatalyst‑sulfur-doped iron polyoxometalate (Fe-POM-S) decorated with zeolitic imidazolate frameworks (ZIF-67) on nickel foam (NF)-was synthesized via a straightforward multi-step process. Comprehensive characterization confirmed the morphology, crystal structure, and elemental composition of the NF/Fe-POM-S/ZIF-67 catalyst. The catalyst showed excellent performance under alkaline conditions for both electrocatalysis and photoelectrocatalysis. It achieved an overpotential of 190 mV for OER under light and 130 mV for HER after calcination at 500 °C, both at 10 mA cm−2. Overall water splitting required a low cell voltage of 1.5 at a current density of 10 mA cm−2. For urea oxidation (UOR) in 1.0 M KOH with 0.5 M urea, the catalyst achieved 10 mA cm−2 at only 1.33 V, with overall urea electrolysis requiring 1.38 V. Notably, the catalyst exhibited exceptional durability, retaining activity for over 48 h with negligible performance loss at current density of 100 mA cm−2. This work presents a facile synthesis strategy for designing high-performance, stable electrocatalysts and photoelectrocatalysts, with significant potential for renewable energy applications.