Ionic liquids are considered as emergent pollutants as these compounds possess high persistence in aqueous solution and toxicity toward aquatic organisms. In this work, the adsorption equilibrium of 27 ionic liquids, with different cation head groups, alkyl chain lengths, and anions, onto ZSM-5 was measured experimentally at several compositions and at temperature 298.15 K and 0.1 MPa. The extensive number of ionic liquids studied allows a comprehensive study on the impact of adsorbate chemical structures toward their adsorption process. The gathered experimental results show that the anions have a dominant effect, when compared to the cation head group and the alkyl chain length, in ruling the adsorption of ionic liquids from aqueous solution onto ZSM-5. The adsorption isotherms reveal that the adsorption process is a combination between Langmuir and Freundlich behaviors, with the latter leading the general process. Moreover, computational modelling using COSMO-RS demonstrates the existence of several molecular forces that rule the adsorption process, reinforcing the idea that the ionic liquid anion rules the adsorption. The results collected in the present work provide new understanding on the molecular mechanism for the development of efficient adsorbents for removal and recovery of ionic liquids from aqueous solution.