Carboxylic acids are not only essential sections of medicinal molecules, natural products and agrochemicals but also basic building blocks for organic synthesis. However, high temperature, expensive catalysts and excess oxidants are normally required for carboxylic acid group transformations. Therefore, more eco-friendly and efficient methods are urgently needed. Organic electrochemistry, as an environmentally friendly and sustainable synthetic method, can potentially avoid the above problems and is favored by more and more organic chemists. This review summarized the recent progress on the electrochemical synthesis of carboxylic acids to construct more complex compounds, emphasizing the development of electrosynthesis methodologies and mechanisms in order to attract more chemists to recognize the importance and applications of electrochemical synthesis.