The synergistic effects of gas agitation and ultrasound on mass transfer between immiscible liquids were investigated in an in-house made ultrasonic microreactor. With the introduction of inert gas (N-2), a three-phase slug flow with slug bubbles either dispersed in continuous aqueous phase or encapsulated in oil plugs was observed. Under ultrasound irradiation, slug bubbles underwent surface wave oscillation and induced agitation in microchannel. In addition, microbubbles were generated by acoustic cavitation, oscillating intensely and resulting in the formation of O/W emulsion. Bubble oscillation (i.e., slug bubbles and microbubbles) as well as emulsification promoted liquid-liquid mass transfer significantly. Extraction of vanillin from aqueous solution to toluene was employed to demonstrate the mass transfer enhancement. Compared with silent operation, both mass transfer coefficient and extraction efficiency were largely improved by the combined use of gas agitation and ultrasound. With gas flow velocity being 0.005-0.083 m/s at fixed ultrasound power of 30 W, the overall mass transfer coefficients ranged from 0.047 s(-1) to 0.429 s(-1), which was 2.33-17.20 times larger than the corresponding liquid-liquid two-phase process without ultrasound irradiation. (C) 2018 Elsevier Ltd. All rights reserved.