Three ruthenium(II) polypyridine complexes of general formula [Ru(bpy)3-n(TTF-dppz)n](PF6)2 (n=1-3, bpy=2,2-bipyridine), with one, two or three redox-active TTF-dppz (4,5-bis(propylthio)tetrathiafulvenyl[i]dipyrido[3,2-a:2,3-c]phenazine) ligands, were synthesised and fully characterised. Their electrochemical and photophysical properties are reported together with those of the reference compounds [Ru(bpy)3](PF6)2, [Ru(dppz)3](PF6)2 and [Ru(bpy)2(dppz)](PF6)2 and the free TTF-dppz ligand. All three complexes show intraligand charge-transfer (ILCT) fluorescence of the TTF-dppz ligand. Remarkably, the complex with n=1 exhibits luminescence from the Ru2+dppz metal-to-ligand charge-transfer (3MLCT) state, whereas for the other two complexes, a radiationless pathway via electron transfer from a second TTF-dppz ligand quenches the 3MLCT luminescence. The TTF fragments as electron donors thus induce a ligand-to-ligand charge-separated (LLCS) state of the form TTF-dppz--Ru2+-dppz-TTF+. The lifetime of this LLCS state is approximately 2.3 s, which is four orders of magnitude longer than that of 0.4 ns for the ILCT state, because recombination of charges on two different ligands is substantially slower.