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The title compound, [Cu(C12H8N2)2]2[W6O19], consists of two [Cu(phen)2]+ cations (phen = 1,10-phenanthroline) and one typical [W6O19]2− isopolyanion. The CuI atom is coordinated by four N atoms from two bidentate chelating phen ligands in a distorted tetrahedral geometry. The hexatungstate anion, lying on an inversion center and possessing the well known Lindqvist structure, is formed by six edge-sharing WO6 octahedra, thus exhibiting an approximate Oh symmetry. Three kinds of O atoms exist in the hexatungstate, viz. terminal Oa, bridging Ob and central Oc atoms. Besides the electrostatic effects between the anions and cations, weak C—H...O hydrogen bonds exist between the phen ligands and Oa or Ob atoms. The mean interplanar distances of 3.485 (1) and 3.344 (1) Å indicate π–π stacking interactions between neighboring phen ligands. These weak hydrogen bonds and π–π stacking interactions lead to a two-dimensional network.