Bismuth goes GaGa: Dibismuthenes are derived from commercially available bismuth(III) triflate or aryloxide salts by employing [Ga(ddp)] (ddp=CH[MeC(2,6-iPr2C6H3)N]2) as an efficient reducing agent and trapping ligand. Apart from the shortest bismuth-bismuth bonds known to date, the compounds demonstrate the unique synthetic potential in main-group chemistry of lowcoordinate Group 13 compounds analogous to N-heterocyclic carbenes. © 2009 Wiley-VCH Verlag GmbH & Co. KGaA.