Observations of intermolecular excimers in several pi-conjugated polymers and exciplexes of these polymers with tris(p-tolyl)amine are reported. It is shown that the luminescence of conjugated polymer thin films originates from excimer emission and that the generally low quantum yield is the result of self-quenching. Thus, in sufficiently dilute solution, the "single-chain" emission has a quantum yield of unity. Exciplex luminescence and exciplex-mediated charge photogeneration have much higher quantum yields than the excimer-mediated photophysical processes. These results provide a basis for understanding and controlling the photophysics of conjugated polymers in terms of supramolecular structure and morphology.