An inorganic-organic hybrid compound {[Cu(phen)3]2PW11VO40 · 2H2O (1) has been hydrothermally prepared and structurally characterized by elemental analyses, IR, CV, TG, magnetic susceptibility measurements and single crystal X-ray diffraction. Compound 1 crystallizes in the monoclinic space group C2/c with a = 27.232(2) Å, b = 25.351(2) Å, c = 16.2748 (4) Å, β = 105.20°, V = 10842.3 Å3, Z = 4, R1 = 0.0490 and wR2 = 0.1362. The structure of 1 exhibits a three-dimensional supramolecular network, formed by hydrogen-bonding and π-π stacking interactions. The three-dimensional network consists of one-dimensional honeycomb channels, which accommodate free water molecules. The size of the channel is 10.4 × 10.4 Å. Electrochemistry of 1 shows it undergoes three one-electron reversible redox processes. Variable-temperature magnetic measurements show typical antiferromagnetic interactions in the 2-300 K temperature range.