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In order to solve the problems of environmental pollution and energy crisis, it is of great significance to develop low-cost, high-efficiency and environmentally friendly multifunctional materials to deal with environmental and energy concerns. Herein, two multifunctional Cu(II) coordination complexes with the formula {[Cu(m-bix)(FDC)(H2O)]·H2O}n (1) and {[Cu2(DAP)4(NIP)2]·DMF}n (2) (m-bix = m-bis(imidazol-1-ylmethyl)benzene; DAP = N-(4-pyridyl)dimethylamine; H2FDC = 2,5-furandicarboxylic acid; H2NIP = 5-nitroisophthalic acid) were successfully constructed by using mixed ligands via a solvothermal method. Structural analyses show that both complexes exhibit a 1D chain structure, extending into a 3D supramolecular network via abundant hydrogen bonding forces. Electrochemical oxygen evolution reaction (OER) catalytic studies reveal that 1 and 2 are efficient electrocatalysts for the OER. In particular, 2 has a lower overpotential of 360 mV at 1 mA cm−2 under alkaline conditions. Furthermore, both complexes exhibit excellent photocatalytic activity due to their narrow band gaps – 2.51 eV (494 nm) for 1 and 2.77 eV (448 nm) for 2. The oxidation system composed of the complex and H2O2 can degrade methyl orange azo dyes (40 mg L−1) to less than 10% in only 150 minutes under sunlight irradiation. This work demonstrates that employing mixed ligands is a promising approach to obtain multifunctional complexes. It also opens up a unique path for the development of high-efficiency, low-cost, and environmentally friendly multifunctional materials to address environmental and energy issues. [ABSTRACT FROM AUTHOR]