The discharge of phenol-containing wastewater has become a crucial and health threatening environmental issue. In this paper, an electro-electrodialysis (EED) process was investigated to remove phenol molecules in the form of phenoxide ions, and simultaneously desalt the laboratory-prepared salty wastewater. The influence of applied voltage, sodium sulfate and phenol concentrations on the separation performance and energy consumption of the EED process was studied. More than 90% of the phenol could be removed, illustrating the feasibility of the EED process. The specific energy consumption for phenol removal was primarily influenced by the concentration and characteristics of the competitive anions, such as sulfate and hydroxide ions in the feed solution. An increase of phenol concentration reduced the specific energy consumption, while a higher salt concentration resulted in higher energy consumption. The EED process is more energy-efficient for treating wastewater with low salt concentrations and high phenol concentrations. These results can significantly enhance the application potential of this emerging separation process.