Electrical properties of poly(epsilon-caprolactone) (PCL)/poly(vinyl butyral) (PVB) blends containing carbon black (CB) were studied as a function of a small amount of PVB content and a wide range of molecular weight of PVB. For samples with the same CB content, the intensity of positive temperature coefficient (I-PTC, defined as the ratio of peak resistivity to resistivity at room temperature) of the blends was increased, with PVB content greatly and molecular weight of PVB weakly. As the band spacings of PCL spherulites in PCL/PVB blends decrease with PVB content and molecular weight of PVB, the changes of the positive temperature coefficient property are ascribed to the morphological difference (i.e., period of twisted lamellae) in the blends. We confirmed our previous conclusion that the origin of the positive temperature coefficient phenomenon is the changes of the distribution of the CB on the melting of the crystalline phase.