An unprecedented cluster [Cu7I11]4– with a pseudo-C3-symmetric cage-like structure has been identified in an ionic salt with [1,4-(Ph3PCH2)2C6H4]2+ cations. The [Cu7I11]4– anion is composed of a six-point star Cu6(µ6-I)(µ2-I)6 capped by a CuI4 tetrahedron. A Cu6 hexagonal subunit of [Cu7I11]4– exhibits strong Cu∙∙∙Cu interactions (dCu–Cu = 2.457–2.958 Å) as evidenced by QTAIM analysis. At 25 °C, the new [Cu7I11]4– cluster emits a weak phosphorescence. In addition, two [Cu2I4]2– iodocuprates supported by [1,4-(Ph3PCH2)2(C6H4)n]2+ cations (n = 1 or 2) are reported, showing no Cu∙∙∙Cu interactions.