Formic acid (FA) has been extensively studied as one of the most promising hydrogen energy carriers today. The catalytic decarboxylation of FA ideally leads to the formation of CO 2 and H 2 that can be applied in fuel cells. A large number of transition‐metal based homogeneous catalysts with high activity and selectivity have been reported for the selective FA dehydrogentaion. In this review, we discussed the recent development of C,N/N,N‐ligand and pincer ligand‐based homogeneous catalysts for the FA dehydrogenation reaction. Some representative catalysts are further evaluated by the CON/COF assessment (catalyst on‐cost number)/(catalyst on‐cost frequency).Conclusive remarks are provided with the future challenges and opportunities.