A study of the electrochemical oxidation of catechol (CA) in the presence of 2-thenoyltrifluoroacetone (TTFA) shows that the electrochemically generated ortho benzoquinone can react with TTFA to form a new derivative of 2-thenoyltrifluoroacetone (TCA) as a final product. Conventional electrosynthesis methods including controlled-potential and constant-current methods in both divided and undivided cells have been used for the synthesis of TCA. In addition, a new approach using an electrolyte-free flow cell has been used for the synthesis of TCA and its results have been compared with those obtained from conventional electrosynthesis methods. The results show that the flow method (89% yield) is superior to the batch methods. The proposed method is a one-pot catalyst-free approach with the ability to synthesize the product with high yield and purity which does not require the use of toxic reagents and solvents.