Magnetic ionic liquids (MILs) have the same features as conventional ionic liquids (ILs), moreover they possess the potentiality of being recovered under the action of permanent magnetic field. Thus, MILs based on imidazolium cations and iron(III) anions were used for the ultrasonic-assisted extraction (UAE) of sinomenine (SIN) from Sinomenium acutum for the first time in this study. The extraction conditions were investigated in the single factor experiments, then the major factors of MIL concentration, liquid/solid ratio, and ultrasonic irradiation time were optimized by response surface methodology (RSM). The extraction yield reached 10.57 mg/g under the optimized conditions. The crude MIL extract of SIN was further purified by reversed micellar extraction (RME) using AOT/isooctane system. The recovery and the purity of SIN reached 81.3% and 82.6%, respectively after purification by RME. This hybrid method of MIL-UAE and RME used for the extraction and purification of SIN was effective, rapid, and potential for scale-up.