This paper investigates the change of the percolation threshold in the carbon powder-filled polystyrene matrix composites based on the experimental results of changes in the resistivity and relative permittivity of the carbon powder filling, the electric field dependence of the current, and the critical exponent of conductivity. In this research, the percolation behavior, the critical exponent of resistivity, and electrical conduction mechanism of the carbon powder-filled polystyrene matrix composites are discussed based on a study of the overall change in the resistivity. It was found that the formation of infinite clusters is interrupted by a tunneling gap in the volume fraction of the carbon powder filling, where the change in the resistivity is extremely large. In addition, it was found that the critical exponent of conductivity for the universal law of conductivity is satisfied if the percolation threshold is estimated at the volume fraction of carbon powder where non-ohmic current behavior becomes ohmic. It was considered that the mechanism for changing the gaps between the carbon powder aggregates into ohmic contacts is identical to that of the connecting conducting phases above the percolation threshold in a random resister network system. The electric field dependence is discussed with a tunneling mechanism. It is concluded that the percolation threshold should be defined at this volume fraction (the second transition of resistivity for the carbon powder-filled polystyrene matrix composites) of carbon powder.