Chloromethylated styrene-divinylbenzene(S-DVB) copolymer beads were prepared in macroporous type via direct copolymerization of chloromethylstyrene and divinylbenzene and then phosphinated. Dichlorotris(triphenylphosphine)ruthenium, RuCl2(PPh3)3, was anchored on the phosphinated S-DVB copolymer, and then applied to the isomerization of 1-hexene. The physical properties of the catalysts varied with degree of crosslinking and type of pore-forming agents. Anchoring the ruthenium complex onto the phosphinated S-DVB resin favored trans-isomer and stabilized the catalyst in the isomerization of 1-hexene comparing with the homogeneous reaction. Solvent effects on catalytic activities of polymer-anchored catalysts were also discussed.