A type of skin-core structured hybrid with a multi-walled carbon nanotube (MWCNT) center was synthesized by in situ free-radical polymerization of vinyl-benzyl ionic liquid and divinylbenzene on the outer surface of MWCNTs. Pt nanoparticles were uniformly deposited on the hybrid using a layer of crosslinked ionic liquid non covalently coated on MWCNTs. The physical characteristics were identified by X-ray diffraction and transmission electron microscopy. The Pt nanoparticles with a small diameter and narrow size distribution were uniformly deposited on the surface of the skin-core structured MWCNTs with an average diameter of 3.3 nm. Cyclic voltammetry results showed that the as-prepared Pt-deposited MWCNT hybrids had a high electrochemical surface area (67.5 m² g⁻¹) and large current density (425.0 mA mg⁻¹) for methanol electrooxidation.