Synthetic electrochemical technologies, which have the potential to transform low-value substrates into valuable products, offer a promising pathway for achieving both environmental remediation and economic benefits. As an alternative to the oxygen evolution reaction in conventional water electrolysis, the pollutant oxidation reaction at the anode can facilitate the simultaneous recovery of value-added products as well as hydrogen evolution at the counter electrode (i.e., cathode). This dual functionality holds promise for potentially addressing the high energy consumption challenges associated with traditional pollutant degradation processes. This review first elucidates the mechanisms of synthetic electrochemical technologies, providing strong evidence for the advantages of generating valuable products in ambient environments in comparison with those produced through traditional chemical pathways. Recent advancements in synthetic electrochemical technologies are then summarized, focusing on the electrochemical treatment of representative contaminants such as 5-hydroxymethylfurfural, lignin, glycerol, glucose, and other refractory organics in wastewater, with the aim of analyzing and summarizing the current research landscape in this field. Specifically, the valuable products from 5-hydroxymethylfurfural and glycerol transformations can be diversified into high- or low-degree oxidation ones according to the oxidation degree of reaction sites. The engineered bond-breaking position of depolymerization products from lignin can achieve the recovery of desired products. Beyond the transformations of representative contaminants, the conversions of other refractory organics such as phenols, chlorinated organics, and nitrobenzene into valuable products are also discussed further. By examining the interplay between the design of catalyst surface structures, the regulation of reaction system conditions, and the activity and selectivity of pollutant conversion reactions, we uncover the structure–activity relationships between catalysts and pollutant transformation. This understanding provides theoretical support for developing highly active catalysts that can enhance the value-added conversion of pollutants. Furthermore, this review conducts a techno-economic analysis of products generated by synthetic electrochemical technology compared with other technologies. We delve into strategies to suppress side reactions that interfere with target pollutant conversion and diminish the purity of value-added products, offering robust evidence supporting the economic viability of synthetic electrochemical technology. Finally, the challenges facing this field and its future developmental prospects are explored in detail. Addressing these challenges requires a multidisciplinary approach, integrating insights from materials science, chemical engineering, and environmental technology. Research efforts need to focus on high flux design and in situ characterization of catalysts, as well as isolation and purification of value-added products for industrial applications. Future work should also consider the integration of synthetic electrochemical technology with machine learning technology to improve efficiency.