With the rapid development of industrial society, phenolic pollutants already identified in water are severe threats to human health. Traditional detection techniques like chromatography are poor in the ability of cost-effectiveness and on-site detection. In recent years, electrochemical enzymatic biosensors have attracted increasing attention for use in the recognition of phenolic compounds, which is considered an effective strategy for the product transfer of portable analytical devices. Although electrochemical enzymatic biosensors provide a fast, accurate on-site detection technique, the difficulties of enzyme deactivation, poor stability and low sensitivity remain to be solved. Thus, effective immobilization methods of enzymes and nanomaterials with excellent properties have been extensively researched to obtain a high-sensitivity and high-stability biosensing platform. Simultaneous detection of multiple phenols may become the focus of further research. In this review, we provide an overview of recent progress toward electrochemical enzymatic biosensors for the detection of phenolic compounds, including enzyme immobilization approaches and advanced nanomaterials, especially nanocomposites with attractive properties such as good conductivity, high specific surface area, and porous structure. We will comprehensively discuss the features and mechanisms of the main enzymes adopted in the construction of different phenolic biosensors, as well as traditional methods (e.g., adsorption, covalent bonding, entrapment, encapsulation, cross-linking) of enzyme immobilization. The most effective method is based on the properties of enzymes, supports and application objective because there is no one-size-fits-all method of enzymatic immobilization. The emphasis will be given to various advanced nanomaterials, including their special nanostructures, preparation methods and performance. Finally, the main challenges in future research on electrochemical phenolic biosensors will be discussed to provide further perspectives for practical applications in dynamic and on-site monitoring. We believe this review will deliver an important inspiration for the construction of novel and high-performance electrochemical biosensors from enzyme selection to nanomaterial design for the detection of various hazardous materials. We believe this review will deliver an important inspiration on the construction of novel and high-performance electrochemical biosensors from the enzyme selection to the nanomaterial design for detections of various hazardous materials.