ABSTRACT Phosphine–phenolate nickel catalysts, based on [P, O] ligand, attracted much attention for its ability in catalyzing the copolymerization of ethylene with polar monomers. Herein, a series of tert ‐butyl substituted phosphine‐phenolate nickel complexes were synthesized and exhibited good catalytic performance in ethylene polymerization. Simultaneously, the molecular weight of the polyethylene products can be altered by steric and electronic perturb. In the copolymerization of ethylene with tert ‐butyl acrylate, methyl 10‐undecenoate and 6‐chlorohex‐1‐ene, these phosphine‐phenolate nickel catalysts yielded copolymers with tunable comonomer incorporation ratio (0.6‐2.0 mol%).