Rational interface engineering to develop highly efficient and durable bifunctional electrocatalysts is of paramount importance for practical alkaline water electrolysis. Herein, we report a conductive poly-metal–organic framework (Poly-MOF)-derived heterostructure electrocatalyst on nickel foam (NF) prepared by a facial drop-coating strategy. The hierarchical porous nanoarchitecture provides abundant electroactive sites, enhanced charge-transfer kinetics, and superior electrolyte accessibility, resulting in excellent electrocatalytic activity for the oxygen evolution reaction (OER) in alkaline media. The optimized Ti-Poly-MOF/NF electrode exhibits an ultralow OER overpotential of 234 mV at 10 mA cm⁻² in 1.0 M KOH, along with a small Tafel slope of 54 mV dec⁻¹, indicating fast reaction kinetics and favorable adsorption/desorption of oxygenated intermediates. The catalyst further demonstrates excellent electrochemical stability during long-duration chronoamperometric operation, with negligible degradation in activity. The enhanced catalytic performance is attributed to the synergistic effects of multi-transition-metal active centers, conductive, interconnected frameworks, defect-rich surfaces, and the three-dimensional porous nickel foam substrate. Moreover, the self-supported, binder-free electrode architecture effectively reduces interfacial resistance and facilitates rapid electron transport during alkaline water splitting. This work presents a promising strategy for designing advanced Ti-Poly-MOF-derived multifunctional electrocatalysts for next-generation sustainable hydrogen production and industrial alkaline electrolyzer applications.