A new type of multiply coated Ni/PSt/TiO2 Composite particles with response to external electric and magnetic fields were presented in the paper. The multilayer complex particles consisted of a metallic nickel (Ni) core encapsulated with a polymeric polystyrene (PSt) and coated with an outlayer of dielectric TiO2. The morphology and structure of the particles were characterized by transmission electron microscopy, scanning electron microscopy, thermogravimetric-differential thermal analysis, X-ray diffraction, and Fourier transform infrared spectroscopy. The resulting composite particles showed good responses to electric and magnetic fields, which was reflected by the formation of a network structure under electric and magnetic fields superimposed perpendicularly.