Polysiloxane/polyolefin copolymers have drawn much attention recently and emerged as a new group of functional polyolefin since they possess distinctive properties and find great potential applications in many areas (eg, compatibilizer, processing aid and surface modifier). However, traditional routes to synthesize polysiloxane/polyolefin copolymers generally require multi-step labor-consuming procedures. Herein, we report a novel one-step synthesis of polydimethylsiloxane graft polyethylene (PDMS-g-PE) mimics. It was found that PDMS-g-PE mimics, namely vinylmethylsiloxanedimethylsiloxane-(C30-45 alkyl)methylsiloxane copolymers (short for VD-AMS), could be formed via a one-step synthetic procedure based on the siloxane equilibrium process between silanol-terminated vinylmethylsiloxane-methylsiloxane copolymer and (C30-45 alkyl)methylsilicone. The chemical structures of VD-AMS were characterized unambiguously using Fourier transform infrared spectroscopy, nuclear magnetic resonance, gel permeation chromatography, differential scanning calorimetry. The correlation between reaction conditions and the structural parameters of VD-AMS was established. Based on our experimental results, a plausible mechanism for the synthesis of VD-AMS was proposed. Scanning electron microscopy micrographs showed that VD-AMS could function as an efficient compatibilizer for immiscible PE/silicone blend.Given that the precursors of VD-AMS are commercially available with low prices and that VD-AMS can be easily synthesized under mild conditions, we believe VD-AMS can represent as a competitive potential compatibilizer due to its relatively low cost. K E Y W O R D S compatibilizer, one-step synthesis, polysiloxane graft polyethylene mimic, siloxane equilibrium process