Tetranuclear [Cu-4(mu(2)-dppm)(3)(mu(2)-mu(2)-NS2)(mu(2)-mu(4)-NS2)] (1) and pentanuclear [Cu-5(mu(2)-dPPM)(4)(mu(3)-mu-(3)-NS2)(2)]PF6 (2.PF6) (dppm = bis-(diphenylphoshino) methane, NS22- = 1,8-naphthalenedithiolate) were synthesized from the reactions between NS22- and [Cu-2(mu(2)-dppm)(2)(CH3CN)(2)](PF6)(2). Compound 1 features a square Cu-4 core capped by a 5-coordinate S atom while 2.PF6 exhibits an unprecedented square planar Cu-5 core. Both complexes display dual emissions at 480 and 620 nm which arise from ligand-centered npi* and ligand-metal charge-transfer excited states, respectively.