A new spin-1/2 frustrated antiferromagnet, Cu9O2(VO4)4Cl2, was synthesized via chemical vapor transport method that emulates mineral formation in volcanic fumaroles. Cu9O2(VO4)4Cl2 is the first copper oxychloride vanadate obtained in the ternary CuO–V2O5–CuCl2 anhydrous system. Copper ions constitute a three-dimensional complex framework with a topological structure novel for synthetic compounds but similar to that in the fumarolic mineral yaroshevskite. All of the oxygen atoms except for the O7 site are strongly bonded in the VO4 tetrahedra. The O7 site belongs to an additional oxygen atom (Oa) being tetrahedrally coordinated by four Cu atoms, thus forming the OCu4 tetrahedra. The structural formula can be represented as Cu3[Cu6O2](VO4)4Cl2 highlighting oxocentered units in the structure. IR spectra reveal several absorption bands at 526, 578, and 601 cm–1 interpreted as a characteristic feature of the OCu4 tetrahedra. Cu9O2(VO4)4Cl2 reveals ferrimagnetic behavior with the Curie temperature TC = 24 K and the uncompensated moment of Mr ∼ 1.9 μB/f.u.