Abstract: Electrocatalysis is a key component of many clean energy technologies that has the potential to store renewable electricity in chemical form. Currently, noble metal-based catalysts are most widely used for improving the conversion efficiency of reactants during the electrocatalytic process. However, drawbacks such as high cost and poor stability seriously hinder their large-scale use in this process and in sustainable energy devices. Carbon-based metal-free catalysts (CMFCs) have received growing attention due to their enormous potential for improving the catalytic performance. This review gives a concise comprehensive overview of recent developments in CMFCs for electrosynthesis. First, the fundamental catalytic mechanisms and design strategies of CMFCs are presented and discussed. Then, a brief overview of various electrosynthesis processes, including the synthesis of hydrogen peroxide, ammonia, chlorine, as well as various carbon- and nitrogen-based compounds is given. Finally, current challenges and prospects for CMFCs are highlighted.