Three novel copper compounds, Rb₄Cu₄OCl₁₀ (I), Rb[Cu₃O](SeO₃)₂Cl (II), and RbCu₃(OH)(SeO₃)Cl₄(H₂O)₃ (III) were prepared by chemical vapor transport (CVT) reactions method from mixtures of CuO, SeO₂, RbCl, and CuCl₂. The crystal structures of the three compounds were determined by direct methods. Compound I is a Rb analogue of ponomarevite, K₄Cu₄OCl₁₀. Its crystal structure contains {[OCu₄]Cl₁₀}^4– clusters with oxocentered [OCu₄]⁶⁺ tetrahedra as cores. The clusters are linked by the Rb⁺ cations. The crystal structure of II contains complex {[O₂Cu₆](SeO₃)₄Cl₂}^2– layers formed by dimers of edge-sharing [OCu₄]⁶⁺ tetrahedra interlinked via selenite groups and Cl^– anions. The crystal structure of III is based upon {[(OH)Cu₃](SeO₃)}³⁺ layers formed by the [(OH)Cu₃]⁵⁺ tetrahedra attached to (SeO₃)^2– groups. The layers are linked via Cl^– anions and via hydrogen bonds to H₂O molecules.