The efficiency of organic photovoltaics is often limited by the poor charge and exciton transport properties of the light harvesting components. Time and angle resolved two photon photoemission is used to directly study the ultrafast properties of the optically excited states in these materials which determine its photoconductivity. Time resolved band structures for both unsubstituted sexithiophene (6T) and (a, ?)-dihexyl-sexithiophene (DH6T) have been obtained on Ag(111). Following the initial excitation, both 6T and DH6T have nearly free electron like dispersions in the LUMO and LUMO+1; however, they have very different temporal evolution. Excitations in 6T decay in 30 fs. In DH6T, many of the electrons interact strongly with the hexane chains to form a bound small polaron which lives for more than 150 fs. The effects on charge transport of adding large, insulating side chains to organic semiconductors will be discussed based on these results.