Rare metal alkoxides, as key precursors for gate dielectric materials in semiconductor chips, particularly involving the oxides of rare metals such as zirconium, hafnium, tantalum, and niobium, play a crucial role in high-tech fields. Although the traditional halide synthesis method for preparing alkoxides has been widely used, it has drawbacks such as complex processes and low yield. In contrast, electrochemical synthesis is gaining attention due to its simpler process and higher yield, offering significant cost advantages over traditional methods and enhancing the economic benefits for related enterprises. The review summaries our group, research over the past two decades on the electrochemical synthesis of zirconium, hafnium, tantalum, and niobium alkoxides was reviewed, including studies on the electrode reaction mechanisms, determination of process parameters, and physicochemical characterization of the products. The aim is to drive the optimization of the electro-synthesis technology for rare metal alkoxides, provide solid technical support to relevant enterprises, and accelerate the rapid development of integration of production, education, research, and application.