To achieve selective recognition of water-soluble ionic compounds, we developed an effective preparation method that can construct specific recognition sites on a cross-linked polymer surface using ionic complexes of functional monomers and template molecules. The specific ionic complexes used for selective recognition were attached on the Surface of cross-linked polymer pores via a reaction between ionic complexes and unreacted vinyl groups on the polymer. In this paper, we show that ionic complexes can attach to the polymer surface by determining the number of unreacted vinyl groups on the cross-linked base polymer. The prepared polymers had greater effective adsorption ability than normally prepared molecularly imprinted polymer because there were no dead sites in the cross-linked network. Furthermore, according to chromatographic evaluations involving frontal analyses, the prepared polymer has selective recognition ability based on the interval recognition of ionic compounds. The adsorption isotherm also suggests selectivity for the template molecule on the prepared polymer. Finally, the paralytic shellfish poison saxitoxin was selectively extracted using the prepared polymer.