Measurements of 'H nuclear magnetic resonance (NMR) and differential scanning calorimetry (DSC) are reported for the composite formed by poly(ethylene oxide) (PEO) and Carbon Black (CB) and the composite polymer electrolytes formed by PEO8LiClO4 and CB. The H-1 NMR lineshapes acid relaxation times (T-1 and T-2) were investigated as a function of temperature and CB concentration. The results suggest that the dynamic behavior of the polymer chains is affected by the presence of the filler.