Pure [Cu(XeF2)(2)](SbF6)(2) was prepared by the reaction of Cu(SbF6)(2) with a stoichiometric amount of XeF2 in anhydrous hydrogen fluoride (aHF) at ambient temperature. The reaction between Cu(SbF6)(2) and XeF2 (1:4 molar ratio) in aHF yielded [Cu(XeF2)(4)](SbF6)(2) contaminated with traces of Xe2F3SbF6 and CuF2. The 6-fold coordination Of Cu2+ in [Cu(XeF2)(2)](SbF6)(2) includes two fluorine atoms from two XeF2 ligands and four fluorine atoms provided by four [SbF6](-) anions. The neighboring [Cu(XeF2)2](2+) moieties are connected via two [SbF6] units, with the bridging fluorine atoms in cis positions, into infinite -[Cu(eta(1)-XeF2)(2)]-(cis-eta(2)-SbF6)(2)-[Cu(eta(1)-XeF2)(2)]-chains. Because of the high electron affinity Of Cu2+, coordinated XeF2 shows the highest distortion (Xe-F-b = 210.2(5) pm, Xe-F-t = 190.6(5) pm) observed so far among all known [Mx+(XeF2)(n)](A)(x) (A = BF4, PF6, etc.) complexes. The four equatorial coordination sites of the Cu2+ ion in [Cu(XeF2)(4)](SbF6)(2) are occupied by four XeF2 ligands, Two fluorine atoms belonging to two [SbF6] units complete the Cu2+ coordination environment. The neighboring [Cu(XeF2)(4)](2+) species are linked via one [SbF6] unit, with bridging fluorine atoms in trans positions, into linear infinite -[Cu(eta(1)-XeF2)(4)]-(trans-eta(2)-SbF6)-[Cu(eta(1)-XeF2)(4)]- chains. To compensate for the remaining positive charge, crystallographically independent [SbF6]- anions are located between the chains and are fixed in the crystal space by weak Xe center dot center dot center dot F(Sb) interactions.