Polyethylene glycol-based polymeric monolithic stationary phases (capillary columns of 0.32 mm I.D.) were successfully prepared via one-pot-single-step reaction and were use in ion chromatography for the separation of several common inorganic anions. It should be noted that the prepared polyethylene glycol-monoliths were able to retain and separate the anions even though there were no ion-exchange sites. The retention mechanism was found to be based on the eluent cations trapped among the polyethylene glycol chains and worked as the anion-exchange sites. Several parameters such as the reaction conditions, monomer:porogen ratios, type of eluents, etc., were investigated. The relative standard deviations obtained for the retention times and signal intensities were less than 5 and 10% respectively. Theoretical plate numbers obtained for the separation of these anions were calculated to be in the range of 700-4300 plates for capillary columns of 10 cm in length.