AbstractIn recent years, flexible electronics technology has been developing rapidly, and flexible electronic devices have been widely used in wearable gadgets and robotics. Flexible wires are the basic components of these devices, which usually consist of metallic materials with flexibility and ductility. However, the introduction of flexible conductive materials has broadened the application scope of flexible wires. In this paper, PDMS/SCF conductive composites exhibiting different conductivity properties on both sides are fabricated by adding meshes based on the continuous spatial‐confining network assembly method. The conductivity of PDMS/SCF (6 wt%) composites can be exhibited as 173.45 S/m in the conductive layer and 6.25 × 10−11 S/m in the insulating layer, which can be used as core and surface layers of conductors, respectively. A mathematical model is also developed to predict the electrical conductivity of the PDMS/SCF conductive composites, and the experimental data are in good agreement with the predicted results. This work provides a method for the continuous preparation of multifunctional composites that can be molded in one step with conductive layer and insulating layer, which can be used as the core and insulating layers of wires, thus simplifying the preparation process of composite‐based wires and expanding the range of conductive composites applications.