The present work studies the electrical conduction performance of carbon black (CB)filled poly(ethylene oxide) (PEO) composites. The addition of CB leads to reduced matrixcrystallinity as the fillers which are partly situated inside the lamellae and hinder the growth of PEOcrystallites. As a result, the electrical percolation behavior is related with the matrix morphology. The present work studies the electrical conduction performance of carbon black (CB) filled poly (ethylene oxide) (PEO) composites. The addition of CB leads to reduced matrix crystallinity as the fillers which are well situated inside the lamellae and hinder the growth of PEOcrystallites. As a result, the electrical percolation behavior is related with the matrix morphology.