A new copper selenite chloride Cu(5)(SeO(3))(4)Cl(2) has been prepared by chemical vapor transport reactions. Its crystal structure was determined by single-crystal X-ray diffraction. The title compound crystallizes in the monoclinic space group P2(1)/c with the unit cell parameters a = 10.9104(8) Å, b = 8.3134(6) Å, c = 7.5490(6) Å, β = 90.715(6)°, Z = 2, and R(1) = 0.0383. Bond valence sum calculations indicate that the cations have the oxidation state Cu(II) and Se(IV), respectively. Three crystallographic different copper atoms, having different coordination polyhedra, [CuO(5)], [CuO(6)], and [CuO(3)Cl(2)], are connected by corner and edge sharing to form a framework that can be described as metal-oxygen slabs connected by Cl atoms via edge sharing [CuO(3)Cl(2)] polyhedra. The two crystallographic different selenium atoms both have [SeO(3)E] coordination, where E is the 4s(2) lone pair on Se(IV); they are isolated from each other and do bond to the Cu-coordination polyhedra only. The magnetic properties of the Cu(2+) ions with effective spin S = 1/2 moments are dominated by antiferromagnetic interactions. For temperatures T < T(c) ∼45 K, Néel magnetic ordering is observed with small ferromagnetic canted moments. We attribute these to antisymmetric Dzyaloshinskii-Moriya (DM) spin exchange which is allowed by the low symmetry spin exchange paths along the distorted transition metal oxyhalide coordinations.