In this study, piperidinium-based ionic liquids (IL) containing trifluoromethanesulfonate, phenolate, and dicyanamide anions were synthesized. Using the ILs, extraction of naphthenic acid from highly acidic oil with a total acid number (TAN) of 1.44 was studied. Two agitation techniques have been implemented for the extraction process, which were mechanical stirring and ultrasonic-assisted irradiation. 1-Butyl-1-methylpiperidinium phenolate BMPiPhe showed the best potential in extracting naphthenic acid from oil, with complete removal of naphthenic acid with IL-to-oil ratios of 0.010 and 0.0025 for the mechanical stirring method and the ultrasonic-assisted method, respectively. Ultrasonic-assisted extraction process shows very good potential in enhancing the extraction efficiency of naphthenic acid. Optimization and study on the effects of ultrasonic parameters, namely, IL-to-oil ratio, ultrasonic amplitude, and time, were studied through response surface methodology (RSM). Using BMPiPhe, the optimum conditions obtained are IL-to-oil ratio of 0.03, 53.91% of amplitude, and 4.29 min of extraction time. Under these optimum conditions, 100% removal of naphthenic acid was achieved. © 2021 The Authors. Published by American Chemical Society.