We report transient photo-induced absorption and reflectivity measurements on poly(2,5-thienylene vinylene), PTV, using the pump and probe technique. We observe a transient photoinduced bleaching of the inter-band absorption with a rise time of 100 fs, limited by our laser pulse duration, and a relaxation time of 2.6±0.2 ps. We observe the same kinetics in transient reflectivity experiments. We relate this response to the very low quantum yield for luminescence to show the importance of non-radiative relaxation pathways in this material. © 1991.