Formic acid (FA) can serve as a hydrogen carrier and is easy to store and transport. However, the decomposition of FA requires the use of a catalyst to accelerate the reaction rate and improve the hydrogen yield, which is of great significance for promoting the development of hydrogen energy technology and achieving sustainable development goals. Herein, chitosan-derived nitrogen-doped biochar-supporting palladium nanoparticles were synthesized and used as catalysts for formic acid dehydrogenation, showing excellent catalytic performance. The initial TOF of the Pd 9.2/C–N catalyst reached 615 mol H2 mol Pd–1 h–1 and the activation energy was 39.15 kJ mol–1. The good catalytic performance of the catalyst was attributed to the well-distributed ultrafine palladium nanoparticles with a size of 2.2–2.6 nm and proper metal-carrier interaction, which enhanced the capability of the palladium nanoparticles in the cleavage of the C–H bond of FA. Parameters, such as palladium loading and reaction time, were investigated along with an improved and comprehensive kinetic study, which provides new insights into the field of FA dehydrogenation.