The polymerization of 2,6-xylenol (XOH) was catalyzed by using a copper complex of a telomer-type surfactant containing 4-vinylpyridine, 1-benzyl-4-vinylpyridinium chloride, and methyl acrylate or styrene (L-VP-Q, L-VP-Q-MA, L-VP-St, and L-VP-Q-St). A copper complex of L2.5VP3.9Q2.2MA catalyzed an emulsion polymerization of XOH more than that of L-VP-Q, 4-vinylpyridine polymer (VP-Q), or pyridine. Furthermore, the oxidative polymerization of XOH in several organic solvents was more effective than emulsion polymerization. The copper complexes formed reversed-micelles in water (3–10 vol%)-DMSO, and the catalytic actions were in the following order: L-VP-Q>VP-Q>pyridine. The acceleration by the L-VP-Q complex was considered to be due to the adsorption of XOH on reversed micelles.