A novel wastewater treatment process, acoustic cavitation assisted plasma (ACAP) is proposed in this study aiming at expanding the treatable range of water pollutants due to a synergetic effect of ultrasound irradiation and high voltage plasma discharge. In this process, the role of acoustic cavitation is not only to provide generation of chemically active OH radicals, as for example in conventional ultrasonic wastewater treatment techniques, but also to ensure conditions for stable plasma generation in wastewater and, thus, to extend the treatable range of water pollutants. Rhodamine B (RhB) was used as a model pollutant in experiments examining effects of ultrasound amplitude, RhB initial concentration, output voltage, solution pH and electrical conductivity on the RhB degradation efficiency. The results revealed that the ultrasound-assisted plasma generation requires lower output voltages and allows to increase the acceptable range of electrical conductivity of treatable solutions up to 1000 μS/cm, that is about 24 times higher than in the case of conventional plasma discharge treatment. The alkaline and acid medium were found to be favorable for higher degradation efficiency. Additional measurements and results of recent investigations concerning underwater plasma showed that microbubbles presented in cavitation zone could serve as "bridges" making the pulse discharge propagation between the electrodes easier than in the conventional case. Besides, acoustic cavitation assists a faster transition of plasma discharge from ineffective streamer type to more effective spark type that further contributes to the improvement of the treatment performance.