The structure of bis[P,P‐di‐tert‐butyl‐N‐(di‐tert‐butylphosphorothioyl)phosphinimidothioato‐κS]sulfur(II) toluene solvate (systematic name: 5,13‐dibutyl‐7,7,11,11‐tetramethyl‐8,9,10‐trithia‐6,12‐diaza‐5λ5,7λ5,11λ5,13λ5‐tetraphosphaheptadeca‐6,11‐diene‐5,13‐dithione toluene solvate), C32H72N2P4S5·C7H8, at 173 K has monoclinic (C2/c) symmetry. The SII centre of (SPtBu2NPtBu2PS–)2S is coordinated in an S‐monodentate fashion to two [(SPtBu2)2N]− monoanions. The molecule resides on a twofold axis which bisects the central S atom. The internal P—S distance is ca 0.19 Å longer than the terminal P=S bond and there is a compensating alternation in P—N bond distances. The central S—S—S angle is 106.79 (8)°. The toluene solvent molecule is disordered about a twofold axis.