We report the preparation of complexes in which ruthenium(II) bis(bipyridyl) groups are coordinated to oligothiophenes via a diphenylphosphine linker and a thienyl sulfur (P,S bonding) to give [Ru(bpy)(2)PT3P,S](PF6)(2) (bpy = 2,2'-bipyridyl, PT3 = 3'-(diphenylphosphino)-2,2':5',2"-terthiophene), [Ru(bpy)(2)PMeT3P,S](PF6)2 (PMeT3 = 3'-(diphenylphosphino)-5-methyl-2,2':5',2"-terthiophene), [Ru(bpy)(2)PMe2T3-P,S](PF6)(2) (PMe2T3 = 5,5"-dimethyl-3'-(diphenylphosphino)-2,2':5',2"-terthiophene), and [Ru(bpy)(2)PDo(2)T(5)-P,S](PF6)(2) (PDo(2)T(5) = 3,3""-didodecyl-3"-diphenylphosphino-2,2':5',2":5",2"':5"',2.....pentath iophene). These complexes react with base, resulting in the complexes [Ru(bpy)(2)PT3-P,C]PF6, [Ru(bpy)(2)PMeT3-P,C]PF6, [Ru(bpy)(2)PMe2T3-P,C]PF6, and [Ru(bpy)(2)PDo(2)T(5)-P,C]PF6, where the thienyl carbon is bonded to ruthenium (P,C bonding). The PC complexes revert back to the P,S bonding mode by reaction with acid; therefore, metal-thienyl bonding is reversibly switchable. The effect of interaction of the metal groups in the different bonding modes with the thienyl backbone is reflected by changes in alignment of the thienyl rings in the solid-state structures of the complexes, the redox potentials, and the pi -> pi* transitions in solution. Methyl substituents attached to the terthiophene groups allow observation of the effect of these substituents on the conformational and electronic properties and aid in assignments of the electrochemical data. The PT ligands bound in PS and P, C bonding modes also alter the electrochemical and spectroscopic properties of the ruthenium bis(bipyridyl) group. Both bonding modes result in quenching of the oligothiophene luminescence. Weak, short-lived Ru -> bipyridyl MLCT-based luminescence is observed for [Ru(bpy)(2)PDo(2)T(5)-P,S](PF6)(2), [Ru(bpy)(2)PT3-P,C]PF6, [Ru(bpy)(2)PMeT3-P,C]PF6, and [Ru(bpy)(2)PMe2T3-P,C]PF6, and no emission is observed for the alternate bonding mode of each complex.