Significant conductive polymer-based composites consisting of immiscible semi-crystalline polymers PP and PVDF, at different volume ratios loaded with a certain concentration of CB were prepared by blending and sequent hot-pressing technology. The distributing status of CB in the polymers was evaluated through the micrographs of the composite. The percolation threshold of this kind of composite is much lower than those of the individual polymers. Even more, the composite at 1/1 volume ratio of PP and PVDF displays the best conductivity among different ratios at a certain concentration of CB, and it displays an outstanding PTC effect more than five orders of magnitude, and synchronously an enhanced dielectric permittivity about 24.9 at 100 Hz. These inimitable properties may owe to the formation of PP/PVDF co-continuous phases and a double-percolation effect in the composite. The novel polymer-based composite with ultra-low percolation threshold, enhanced PTC effect, as well as the significant dielectric permittivity is promising a potential application.