Faraday and Kolbe's electrolysis of carboxylic acids is known to be the first reported electrochemical reaction involving the synthesis of organic molecules. Even though numerous electrochemical transformations have been developed, organic electrochemistry has remained underemployed in synthesis for a long time. Nevertheless, the growing need to look for greener and more affordable alternatives to classic synthetic methodologies has recently reinvigorated the interest in this old discipline. In this chapter, the main aspects of the Kolbe and non-Kolbe electrolysis will be discussed. It will also be shown how, almost 200 years after its discovery, the electrolysis of carboxylic acids still offers an incredible variety of synthetic opportunities.