The use of formic acid (FA) to produce molecular H2 is a promising means of efficient energy storage in a fuel‐cell‐based hydrogen economy. To date, there has been a lack of heterogeneous catalyst systems that are sufficiently active, selective, and stable for clean H2 production by FA decomposition at room temperature. For the first time, we report that flexible pyridinic‐N‐doped carbon hybrids as support materials can significantly boost the efficiency of palladium nanoparticle for H2 generation; this is due to prominent surface electronic modulation. Under mild conditions, the optimized engineered Pd/CN0.25 catalyst exhibited high performance in both FA dehydrogenation (achieving almost full conversion, and a turnover frequency of 5530 h−1 at 25 °C) and the reversible process of CO2 hydrogenation into FA. This system can lead to a full carbon‐neutral energy cycle. Pyridinic‐N‐tuned catalysis: An electron‐rich pyridinic‐N dopant modulates the electronic interactions between the active sites of palladium nanoparticles and the carbon support. Formic acid dehydrogenation at room temperature is significantly boosted by the pyridinic‐N‐doped palladium catalyst, presenting an efficient and reliable route to clean H2 generation and sustainable energy storage.