Films of poly‐(2‐phenyl‐1,4‐phenylene‐vinylene) (PPPV) and photodiodes with PPPV as an active layer were studied by optically (ODMR) and electrically (EDMR) detected electron‐spin resonance (ESR). Two different signals were observed in ODMR: enhancement of the photoluminescence (PL) atg=2.01 due to recombination of the photogenerated polarons (s=1/2), and a half‐field enhancement signal, attributed to the fusion of triplet excitons. Both processes lead to the formation of singlet excitons. The spectral dependence of thes=1/2 signal follows the low energy part of the PL spectrum, indicating that delayed recombination of distant polarons is influenced by ESR, whereas the cw PL contains both prompt and delayed contributions. The linewidth and the intensity of the ODMR signal depend on the PL excitation intensity. Both effects are due to a decrease of the recombination lifetime of the polaron pairs at higher intensities. The relative decrease of the short‐circuit photocurrentISCthrough a PPPV photodiode by ESR saturation is due to recombination of nonthermalized, nongeminate excess charge polarons in the active layer of the device. This effect is at least two orders of magnitude stronger than the enhancement of total PL at the same temperature. This feature is found to be common for conjugated polymers investigated so far, and reflects the fact that the total photogeneratedISCis spin dependent, whereas ODMR selects only the nongeminate portion of recombining species in the sample. ©1996 American Institute of Physics.