Photoexcitation of a bis(bipyridyl) Ru(II) complex bearing a phosphinopentathiophene ligand results in formation of a transient species with a lifetime of 2.2 As. The transient is attributed to the product of an intramolecular charge transfer from the pentathiophene ligand. EPR and UV/vis spectroelectrochemistry show that the HOMO is pentathienyl-based, while corresponding complexes with shorter conjugation length ligands have a metal-based HOMO and do not exhibit long-lived transients.