Copolymer membranes composed of chloromethylstyrene and divinylbenzene were reacted with 4-vinylpyridine and then trimethylamine to prepare highly tight anion exchange membranes. When 4-vinylpyridine reacted with chloromethyl groups of the copolymer membranes, 4-vinylpyridine polymerized in the membrane matrix to form a ladder-like polymer, of which one polymer was cross-linked. Consequently, relationships of ion exchange capacity and water content to electrical resistance of the obtained membranes were completely different from those of the anion exchange membranes with benzyl trimethylammonium groups cross-linked with divinylbenzene. With increasing reaction time of the copolymer membranes with 4-vinylpyridine, the electrical resistance of the membranes markedly increased with a small decrease in ion exchange capacity and with the decrease in water content. And fixed ion concentration of the membranes reacted with 4-vinylpyridine and then trimethylamine was higher than that of the membranes with benzyl trimethylammonium groups. These are thought to be because of the formation of a ladder-like polymer in the membrane matrix and the introduction of pyridine unit, which is more hydrophobic and bulkier than trimethylamine. The remarkable decrease in the pore size of the membranes was confirmed by the measurement of the diffusion coefficient of neutral molecules, urea and glucose, through the membranes.