Poly(styrene/divinylbenzene) resin with cryptand 22 as an anchoring group was synthesized and applied in ion chromatography as a packing material for separations of organic anions as well as cations. The cryptand can not only form strong complexes with metal cations, but it has also shown a remarkable complexing ability with organic anions after protonation at pH < 7. The protonated cryptand resin has been applied as an anion exchanger to successfully separate some organic carboxylate anions including HCOO-, CH3COO-, CH3CH2COO-, and CH3(CH2)(2)COO-, and some geometric isomers, e.g., fumarate and maleate ions, with water as the eluent. Alternatively, after deprotonated at pH > 7, the cryptand resin can be switched as a cation exchanger to separate inorganic cations. The effects of solvents, temperature, pH values, and flow rates of eluents on the separation of organic anions were also investigated.