How to improve the electrical properties of conductive polymer composite (CPC) such as lowering the percolation threshold and endowing the composite with unique properties is a most important research area in developing this kind of material. Various methods have been employed, among which changing the processing procedure of the material is the most simple. The present paper describes how the authors, by eliminating the mixing procedure before compression moulding, managed to fabricate a material with different percolation thresholds and much more stable volume resistivity temperature behaviours compared to that utilising the mixing procedure. Microstructures of these two materials were investigated. The authors found that the composite produced using the mixing procedure had much shorter conductive fibrils, while that produced without mixing had a hierarchical structure, in which long and well defined conductive fibrils composing the conductive sheet structure first and conductive sheet overlapped together to form the conductive network throughout the composite.