The preparation of N-methyl,N-phenyl-dithiocarbamate mononuclear rhodium(I) complexes is described, and their capability to act as metalloligands for the controlled construction of binuclear dithiocarbamate-bridged species of general formula [Rh-2{mu-S2CN(Me)(Ph)}(COD)L-2]BF4 is investigated. Although in the mononuclear complexes the dithiocarbamate group coordinates as an S,S'-chelate ligand, in the reported binuclear compounds this ligand shows a novel bridging eta(2),eta(2)(S,S') coordination mode. EHT calculations based on these binuclear complexes indicate the intermetallic symmetric mu-eta,(2) eta(2)(S,S') coordination to be the most stable situation.