Wastewater treatment significantly contributes to greenhouse gas emissions, which are further exacerbated by the environmental impact of external chemical additions. In response, microbial electrochemical wastewater refining has gained prominence at the interdisciplinary frontier of wastewater resource recovery and green bio-manufacturing. Significant progress has been made in utilizing active electrodes to stimulate CO₂ fixation rates, applying “binary electron donors” to produce high-value-added chemicals, and developing novel processes and equipment. This review explores various aspects of microbial electrochemical wastewater refining, including microbial electrochemical monitoring of water quality, chemical synthesis from diverse carbon sources, and the deployment of pilot-scale systems for generating electricity, hydrogen, and methane, as well as for in-situ remediation. Additionally, it discusses the challenges and future directions, highlighting the importance of understanding mechanisms, advancing electrocatalyst and microbial engineering, and innovating hybrid processes. In conclusion, the widespread adoption of microbial electrochemical wastewater refining is emphasized for resource recovery and sustainable chemical production, ultimately reducing environmental impact.