A novel VIV‐CuII hybrid complex assembled from an O,O‐chelating vanadium block [VO(2,3‐DHN)2]2– and a N,N‐chelating copper block [Cu(1,3‐PDA)2]2+, namely, [VO(2,3‐DHN)2][Cu(1,3‐PDA)2]·0.5CH3CN (1) (2,3‐DHN = 2,3‐dihydroxynaphthalene, 1,3‐PDA = 1,3‐propanediamine), was synthesized at 8 °C (low room temperature) and characterized by IR spectroscopy and single‐crystal X‐ray diffraction. The vanadium and copper blocks are both independent complexes and are interlinked through N–H···O hydrogen bonds donated by [Cu(1,3‐PDA)2]2+ moiety, exhibiting 1D chain, 2D layer, and open 3D channel supramolecular array. This work was originally sparked by the tunicate chemistry and the [VO(2, 3‐DHN)2]2– ion can be seen a sequel of vanadium‐catechol models.