We contrast the generation and decay of charged and neutral photoexcitations in oriented samples of poly(p-phenylene vinylene). Charge separation is the result of interchain electron motion and is detected through measurement of photoinduced absorption (PA). In contrast, photoexcitation within a single chain results in a short-lived neutral polaron-exciton which is observed by its luminescence if it decays radiatively. We find big differences between the bipolarons detected in the PA experiments (which are extensively delocalized along the chain and are w]eakly confined) and the polaron-excitons (which show very strong confinement and a small Stokes' shift in luminescence). This is not explained within one-electron theories for polaron formation and is, we consider, firm evidence for the importance of Coulomb interactions. © 1989.