8-Arylnaphthyl substituents are privileged motifs frequently integrated into late-transition-metal catalysts, endowing them with an ability to retard chain transfer in ethylene polymerization. In this contribution, we disclose a sort of novel α-diiminenickel and -palladium complexes containing flexible 8-alkylnaphthyl in lieu of rigid 8-arylnaphthyl and their catalytic performance in ethylene polymerization. An interesting feature of these 8-alkylnaphthyl-substituted α-(diimine)PdMeCl complexes is that they present as a mixture of syn and anti isomers (syn:anti = ca. 1:1 ratio, determined by 1H and 13C NMR spectroscopy). In ethylene polymerization, these nickel complexes displayed high activity (up to 3.37 × 106 g mol-1 h-1) and generated branched polyethylenes with broad or bimodal molecular weight distributions (4.6-29.3), while the corresponding palladium complexes exhibited moderate activity, producing highly branched polyethylenes with unimodal and narrow molecular weight distributions (<1.8). In ethylene (E)/methyl acrylate (MA) copolymerization, highly branched E-MA copolymers with considerable MA incorporations were achieved by these palladium complexes. Most interestingly, compared to rigid 8-arylnaphthyl-substituted α-diiminenickel and -palladium complexes, the flexible 8-alkylnaphthyl ones showed significantly improved activity and generated lower or comparable molecular weight polyethylenes or E-MA copolymers.