The acetylene black/silica composite particles were prepared by a simple and fast method using polyethylenimine (PEI) as a coupling agent. The composite particles were produced via the following two steps; adsorption of PEI on the surface of acetylene black particles and synthesis of silica by sol-gel process. The morphology of the composite particles was a core-shell, and a large number of micropores was created after silica was synthesized on the acetylene black surface.