<p>A green and efficient synthesis of novel cyclohexanone diesters was achieved via the double addition of dimethylmalonate to dibenzylideneacetone derivatives in the presence of imidazolium-based ionic liquids as catalysts, without the use of any base. Ionic liquids were synthesized by anion exchange with various organic acid salts. The reaction was optimized by evaluating the effects of various ionic liquids. Among the tested ionic liquids, 1,3-dibutyl-2-methylimidazolium hydroxide ([Dbmim][OH]) demonstrated the highest catalytic performance, yielding up to 99% of the desired products in ethanol as the solvent. The study highlighted the remarkable dual benefits of ionic liquids, showcasing their outstanding catalytic efficiency along with significant environmental advantages, positioning them as a sustainable, eco-friendly, and reusable alternative for the base-free synthesis of cyclohexanone diesters.</p> Graphical abstract <p></p>