Since few examples of 10,11-didehydrogenated (3-ethynyl) cinchona alkaloids have been utilized as organocatalysts in asymmetric reaction, we synthesized 10,11-didehydrogenated cinchonidine. The 3-vinyl group of cinchonidine was transformed into a 3-ethynyl functionality. Based on the resulting 10,11-didehydrogenated cinchonidine, the corresponding quaternary ammonium salt and its dimers were prepared. The ion-exchange reaction between the quaternary ammonium salt and sodium sulfonate produced the quaternary ammonium sulfonate as a stable ionic compound. Chiral ionic polymers were then synthesized by the ion-exchange polymerization of the 10,11-didehydrogenated cinchonidinium salt dimer and a disulfonate. The chiral ionic polymers were found to be capable of efficiently catalyzing the asymmetric alkylation of N-(diphenylmethylene)glycine tert-butyl ester. The enantioselectivities obtained with the polymeric catalysts were higher than those obtained with the corresponding monomeric catalyst. Dimers of 10,11-didehydrogenated cinchonidinium salts were prepared. Treatment of the dimer with disodium disulfonate gave the chiral ionic polymers, which showed high catalytic activity in asymmetric benzylation of N-(diphenylmethylen)glycine tert-butyl ester. The polymeric catalysts were reused several times without the loss of catalytic activity. (c) 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 621-627