Ionic polymers have been proven to be promising adsorbents in recovering Au(III) due to their advantages of simple synthesis and high adsorption efficiency. However, the unclarity of the relationship between the adsorption ability of ionic polymers and their cationic structures hinders further optimization of their adsorption performance. This study synthesized a series of ionic polymers with pyridinium, imidazolium, piperidinium, pyrrolidinium, and triethylammonium cations to discover the effects of the cationic structure on their adsorption properties. Experimental results show that the existence of anion-π interaction between aromatic cations and [AuCl4]- makes the aromatic cations-anion interaction stronger, which does not enhance the adsorption performance of the aromatic-based ionic polymer. This is due to the charge delocalization in the aromatic ring, resulting in a lower electrostatic potential (ESP) of aromatic cations than that of aliphatic cations with a localized charge. The higher the ESP of cations, the better the adsorption performance of the corresponding ionic polymer. This study serves as a deep understanding of the cationic structure-adsorptive performance relationship of the ionic polymer at the molecular level and further provides a theoretical guidance to optimize the adsorption performance of ionic polymers.