Ionically modified ${eta}$-cyclodextrins, which have excellent water-solubility, have been interested in purification technology as well as drug carrier system. The present study summarizes the synthesis and characterization of cationic and anionic ${eta}$-cyclodextrin (${eta}$-CyD) products using by polycondensation. The oligo (${eta}$-CyD)s are synthesized from ${eta}$-CyD, epichlorohydrin (EP) and choline chloride (CC; for cationic polymer) or chloroacetic acid (CAA; for anionic polymer) through one step polycondenstaion process. Unlike the previous studies, we successfully purified the ionic ${eta}$-CyD condensation products from the ${eta}$-CyD reaction mixtures and accomplished a great level of structural analysis. The detailed structural analysis of these ionic ${eta}$-CyD compounds is done by $^1H$ NMR, MALDI-TOF as well as GPC analysis and confirms the formation of oligomers with a few units of ${eta}$-CyD. We found that the sequence of reactant addition also could effect on the molecular weight of the resulting product as well as the molar ratio of the reactants. Finally, we used the cationic and anionic ${eta}$-CyD oligomers for fabricating multilayer films by layer-layer process.