A promising potential new electrocatalyst for water splitting could be developed through the meticulous design and synthesis of diverse bimetallic metal−organic frameworks (MOFs). These MOFs would use different or the same metals from the d and f blocks and could have different oxidation states. This study focuses on developing an efficient bimetallic electrocatalyst, based on the rare-earth lanthanide series element europium (Eu) and transition-metal copper (Cu) as the MOF using a one-pot hydrothermal method. As a result, a significant 4f−3d heterovalent heterobimetallic MOF was obtained, and its electrocatalytic activity toward water splitting was evaluated. Further, heterobimetallic MOFs with their mixed valence display an improved water-splitting performance through synergistic effects. Linear-sweep voltammetry (LSV) studies reveal that the bimetallic Eu−Cu-MOF required an overpotential of 133 mV for hydrogen evolution reaction (HER) and 240 mV for oxygen evolution reaction (OER) at a current density of 20 mA cm −2 in 0.5 M H 2 SO 4 and 1 M KOH, respectively. Moreover, the long-term stability study exhibits a stable nature up to 20 and 16 h in 1 M KOH and 0.5 M H 2 SO 4 solutions, respectively. The incorporation of Eu synergistically increases the adsorption and desorption ability of OH − and O 2 molecules toward OER, respectively. The bimetallic MOF displayed excellent stability under acidic as well as alkaline conditions, indicating an exciting future for Eu−Cu-MOF in the field of electrochemical water splitting.