Conductive polymer matrix composites have been a focus of research for the past 30 years, due to applications such as electromagnetic shielding. The electrical resistance of these materials can be broken into three major categories: the intrinsic resistance of the filler and matrix, the particle‐particle contact resistance, and the tunneling resistance. Both the particle‐particle contact and tunneling resistance in nickel filled low density polyethylene (LDPE) composites can be reduced by the addition of an ultrathin polypyrrole (PPy) coating on the nickel surface. Coating the nickel particles with PPy leads to increases in conductivity as much as three order of magnitude at concentrations well above the percolation threshold without significantly changing the mechanical properties. We believe at concentrations above the critical region PPy forms “molecular wires” reducing the loss of conductivity associated with the uniaxial orientation of the polymer matrix.