Hydrozirconation on vinyl‐terminated substrates (silicon wafer and nanosilica sphere) is employed as an efficient way for immobilization of zirconocene catalyst through Zr? C bonds, which is applied in surface coordination ethylene polymerization producing surface‐tethered polyethylene (PE). The formation of Zr? C σ bond induced by hydrozirconation provides an initiator precursor for growing a layer of PE covalently linked onto substrates. The results from SEM, AFM, and TEM show that the surface polymerization is controlled by hydrozirconation. Surface pattern or core–shell structure with crystalline PE coating can be formed, when silicon wafer is selectively functionalized with vinyl‐groups or vinyl‐modified nanosilica is applied. It is believed that hydrozirconation for the synthesis of zirconocene initiator can be a versatile route to prepare polyolefin hybrid materials.
