An unprecedented microwave C(sp(2))-S and S-S bond activation of 2,2'-dipyridyldisulfide (2-dpds) and the formation of a new architecture of coordination networks obtained by reaction of Cu(HCO(2))(2).xH(2)O with 2-dpds under solvothermal microwave conditions are reported. This unusual reaction proceeds with the partial oxidation of 2,2'-dipyridyldisulfide to sulfate. The process generates: a Cu(I) dimetallic complex [Cu(2)(mu-Hpyt)(2)(Hpyt)(4)](SO(4)).approximately 5EtOH (1), a Cu(I,II) polycationic coordination polymer [Cu(H(2)O)(6)][Cu(6)(mu-Hpyt)(12)](SO(4))(4).4H(2)O (2) and a dimetallic Cu(II) complex [Cu(2-dps)(mu-SO(4))(H(2)O)](2).3H(2)O (3). It is worth mentioning the strong red luminescence shown by compounds 1 and 2.