A novel N-heterocyclic tridentate polycarbene ligand has been synthesized and stabilized as its corresponding silver complex. An electronic structure investigation reveals significant pi-bonding interactions within the Ag-carbene unit of the [(TIMEMe)2Ag3]3+ cation. Thus, reaction of [1,1,1-tris(3-methylimidazolium-1-yl)methyl]ethane tribromide (1a; {[TIMEMe](Br)3}, prepd. via reaction of 1,1,1-tris(bromomethyl)ethane with N-methylimidazole) with NH4PF6 in MeOH gave [TIMEMe](PF6)3 (1b). Reaction of 1a and 1b with Ag2O in DMSO gave title compds., [(TIMEMe)2Ag3](Ag8Br14) (2a) and [(TIMEMe)2Ag3](PF6)3 (2b) resp. The crystal structures of 1a, 2a, and 2b were detd. and electronic structures via DFT calcns. were discussed. [on SciFinder (R)]