Based on the newly designed ligand 4′-(3,5-dicarboxyphenyl)-4,2′:6′,4′′-terpyridine (DCTP), a unique semi-conductive 3D framework {[Cu^ΙCu^ΙΙ₂(DCTP)₂]NO₃⋅1.5 DMF}_n (1) with a narrow band gap of 2.1 eV, was obtained and structurally characterized. DFT calculations with van de Waals correction employed to explore the electronic structure of 1, clearly revealed its semi-conductive behavior. Furthermore, we found that 1 exhibits a superior band alignment with water to produce hydrogen and degrade organic pollutants. Without adding any photosensitizers, 1 displays an efficiently photocatalytic hydrogen production in water based on the photo-generated electrons under UV/Vis light. 1 also exhibits excellent photo-degradation of methyl blue under visible-light owing to the strong oxidization of excited holes. It is the first example of MOFs with doubly photocatalytic activities related to photo-generated electrons and holes, respectively.