A series of 3,3′-pyrrolidonyl spirooxindole derivatives have been synthesized in good yields from the cascade Knoevenagel–Michael–cyclization multicomponent reaction of isatin, malononitrile and α-isothiocyanato imide in the presence of a catalytic amount of triethylamine “on water” assisted with ultrasonic irradiation. The advantages of this method include high efficiency, mild reaction conditions and environmentally benign reagents. The current process provides a simple and green method for creating diversity-oriented syntheses of this intriguing class of compounds with potential biological activities.