A series of phosphine-sulfonate ligands and the corresponding nickel complexes are prepared and characterized. These ligands are specifically designed to bear systematically varied electron-donating and -withdrawing substituents (H, OMe, NMe2, CF3, and Me). More importantly, these substituents are installed at different positions on the ligand framework, namely, the para-position of the phenylphosphino group (position X), and para to the arylsulfonate group of the main ligand (position Y). These nickel complexes are highly active single-component catalysts for the polymerization of ethylene. An electron-donating substituent at position X or an electron-withdrawing substituent at position Y is beneficial to the properties of these nickel catalysts. Specifically, the catalyst bearing the NMe2 substituent at position X exhibits high stability and high activity (3.3 X 10(6) g mol(-)(1) h(-1)), and catalyzes the formation of polyethylene of high molecular weight (M-n 405 000) and high melting point (T(m )138.5 degrees C). This catalyst also mediates the efficient copolymerizations of ethylene with methyl 10-undecenoate, 6-chloro-1-hexene, and trimethoxyvinylsilane.