In this work the electron spin resonance (ESR) and electron detected magnetic resonance (EDMR) are applied in MH-PPV and MEH-PPV, respectively. The ESR measurements revealed that there is a change of lineshape and a clear reduction of spin density on MH-PPV degraded by light and air. This result is in agreement with the fact that the spin density resides predominantly on vinylic carbon. The EDMR measurements in MEH-PPV LEDs provided evidences that there is a spin-dependent fusion of two polarons to spinless bipolaron.