Abstract: The copolymers of ethylene and vinyltriethoxy-silane (VTEoS) can be prepared by α-diimide nickel catalysts with different structures under the activation of EASC via the coordination copolymerization method. In this paper, the effects of VTEoS concentration, catalyst dosage, Al/Ni molar ratio, ethylene pressure, polymerization time, solvent and catalyst structure on copolymerization were studied, and the optimal polymerization conditions were obtained. The copolymer structure, its thermal stability, the content of silicon in the copolymer and the surface properties of the ethylene/VTEoS copolymer film were characterized by nuclear magnetic resonance (¹H-NMR), Attenuated total internal reflectance Fourier infrared spectroscopy (ATR-FTIR), thermogravimetric analysis (TGA), baking and measuring the contact angle of the film. The results showed that the highest catalytic activity reaches 9.10 × 10⁵ g/(mol·h) with C4 as the catalyst in methylene chloride, and the mass content of silicon in the copolymers was in a range of 0.74%—3.39%. The results suggest that introducing silicon-containing monomer into polyethylene chains can enhance the thermal stability and the hydrophobicity of the corresponding copolymer film.