Multiple interfaces and phases between the electrode and electrolyte play a key role in prompting the overall electrocatalysis, due to the high chances of the formation and cleavage of chemical bonds. Here, we employed the most common tactic of coupling functional components into a hybrid heterostructure with improved synergistic effects between organic and inorganics. The functional metal nodes-organic bridge ligands integrated on polyvalent tungsten oxide–carbide interfaces with highly-porous nano-dendritic architectonic is developed. The FeCu–BTC/WO3–WC showed excellent electrochemical half-cell (HER/OER/ORR), and Full-cell (aqueous ZAB and water electrolysis) performances with Ε1/2, ORR = 0.81 V, η10, OER = 249 mV, η10, HER = 99 mV, Ε10, water splitting = 1.531 V, and PDZAB = 135.2 mW cm−2 with profound durability. Hence, the multi-interfacial dendritic FeCu–BTC/WO3–WC ternary nanocomposite offers the prospect of a good harbinger for aggressive reform of energy technologies towards the zero-emission energy goal.