Herein a facile and controllable heterocoagulation between polystyrene(PS) microspheres and multiwalled carbon nanotubes(MWCNTs) is introduced based on colloid thermodynamics. The MWCNTs play the role of steric stabilizer for stabilizing the metastable PS microspheres and thus immobilize spontaneously on the surface of PS microspheres. The synthesized MWCNTs-coated PS composite particles have been extensively characterized by scanning electron microscopy, transmission electron microscopy, thermogravimetry and Raman spectroscopy. The results indicate that the structure and morphology of the resultant MWCNTs-coated PS composite particles are significantly affected by the weight ratio of PS and MWNCTs and the amount of poly(vinylpyrrolidone) that is injected into PS dispersion before they are mixed with MWCNTs. Therefore, these composite particles have the potential to produce MWCNTs-based composite materials with controllable mass loading and dispersity of MWCNTs. Herein a facile and controllable heterocoagulation between polystyrene (PS) microspheres and multiwalled carbon nanotubes (MWCNTs) is introduced based on colloid thermodynamics. The MWCNTs play the role of steric stabilizers for stabilizing the metastable PS microspheres and thus immobilize spontaneously on the surface of PS microspheres . The synthesized MWCNTs-coated PS composite particles have been extensively characterized by scanning electron microscopy, transmission electron microscopy, thermogravimetry and Raman spectroscopy. The results that same structure and morphology of the resultant MWCNTs-coated PS composite particles are significantly affected by the weight ratio of PS and MWNCTs and the amount of poly (vinylpyrrolidone) that is injected into PS dispersion before they are mixed with MWCNTs. Thus, these composite particles have the potential to produce MWCNTs-based composite materials with controllable mass loading and dispersity of MWCNTs.