2,3,6,7,14,15-Hexamethyl-9,10-distibatriptycene (3) reacted with bromine to give an adduct 4 with the composition of 3(.)2Br(2). X-ray structure analysis and H-1 NMR studies revealed that the bromine adduct 4 forms an intramolecular salt composed of a tetracoordinate bromostibonium ion moiety, R3SbBr+, and a hexacoordinate tribromostiborate ion moiety, R3SbBr3-, both in the crystalline state and in solution.