The orthorhombic crystal structure of Cu₄O₂[(As,V)O₄]C1, a = 5.440(1) Å, b = 11.154(2) Å, c = 10.333(2) Å, V = 627.0(3) ų, Z = 4, Pbcm, has been solved by direct methods and refined to an R(F) index of 0.049 (wR(F²) = 0.048). The structure is based on unbranched vierer chains {uB, 1¹_∞} [O₄Cu₈] running parallel to the c axis, which are composed of oxocentered tetrahedra [OCu₄] linked via opposite edges. The chains are bent by the large chloride ions in zigzag fashion so that the periodicity of the chains is equal to four. [(As,V)O₄] groups are located between the puckered chains of oxocentered tetrahedra and crosslink them into layers parallel to the (100) plane, which are held together by the Cu-O_As/V bonds.