The compound bis{μ3-2,5-bis[N-(4-isopropylphenyl)-P,P-diphenylphosphorimidoyl]pyrrol-1-ido-κ3 N:N′:N′′}trisilver(I) trifluoromethanesulfonate deuterated benzene pentasolvate, [Ag3(C46H44N3P2)2](CF3O3S)·5C6D6, (I), was synthesized from two equivalents of NaL [L = 2,5-(4- i PrC6H4N=PPh2)C4H2N] and three equivalents of AgOTf (OTf = OSO2CF3). High-quality crystals of (I) formed with five deuterated benzene solvent molecules in the asymmetric unit. Notably, the bond lengths and angles between the three silver atoms are markedly different, unlike in most other reported trisilver complexes that tend to form three equivalent metal centers. Additionally, to the best of our knowledge, this is the first report of a trisilver complex with six nitrogen donors from two bisphosphinimine ligands.