In this Communication, the copolymerization of ethylene with a sterically hindered α‐olefin comonomer, γ-trisubstituted 3,3‐dimethyl-1-butene (DMB), using a chain‐walking Pd‐diimine catalyst, [(ArN?C(Me)?(Me)C?NAr)Pd(CH₃)(N?CMe)]SbF₆ (Ar?2,6-(iPr)₂C₆H₃) (1) is reported. In spite of its high steric bulkiness in the close proximity of the double bond, appreciable DMB incorporations (up to 3?mol‐%) are successfully achieved in the copolymers. The chain microstructure of the copolymers is elucidated, and the effect of DMB incorporation on polymer topology and thermal properties are examined. This work thus demonstrates the high capability of the Pd‐diimine catalyst in incorporating sterically encumbered α‐olefins.