The electrical conductivity, current-voltage characteristics and morphology of carbon black–filled immiscible blends of poly(vinylidene fluoride)(PVDF) and high density polyethylene (HDPF) were investigated. Carbon black (CB) had stronger affinity to HDPE than to PVDF, resulting in its selective localization in the HDPE phase. The CB content and PVDF/HDPE volume ratio were the two main factors influencing the electrical conductivity, current-voltage characteristics, and morphology. At a fixed PVDF/HDPE volume ratio of 1/1, a percolation threshold of 0.037 volume fraction of CB was observed, and that value was much lower than that for conventional CB-filled polymer composites. At a fixed CB content (10 wt% CB), a maximum electrical conductivity was observed at a PVDF/HDPE volume ratio of 2.75. An increase in CB content in the composites with a fixed PVDF/HDPE volume ratio (1/1) and an increase in PVDF content in composites with a fixed CB content (10 wt%) greatly decreased the domain size of the PVDF phase. A positive-temperature-coefficient effect was used to determine the location of CB in the blends.