Abstract: The expanded graphite (EG) was prepared by microwave irradiation, through solid state shear milling (S³M) with EG, chlorinated polyethylene (CPE) and polyvinyl chloride (PVC), EG-CPE-PVC co-powders were prepared.The co-powders were then mixed homogeneous with PVC, thermal stabilizer and plasticizer.And the graphene-like/CPE-PVC composites were obtained by plastification and molding.Structure and properties of co-powders and composites were characterized by analysis of particle size and distribution, XRD, AFM, SEM and TEM.Results show that S³M can realize pulverizing, dispersion, exfoliation of EG layer and nano-compounding of EG-CPE-PVC.Further more, the addition of CPE realizes the further exfoliation of EG, which makes the EG thickness reaches to 1-3 layers and achieves the goal of transforming EG to graphene.When the EG mass fraction reaches 3%, compared with PVC, the conductivity of graphene-like/CPE-PVC composites shows exponential rise and increases 8 orders of magnitude, while EG mass fraction is over 4%, the conductivity surges again and appears the percolation phenomenon.When the EG mass fraction reaches 5%, the conductivity is up to 0.01 S/m, and the composites show good antistatic property.