Hydrogen release from formic acid is a significant energy supply route. However, the current catalysts suffer from low catalytic efficiency and stability. Herein, a porous N-doped carbon material with high N content (16.87%) and a large surface area (1544 m2·g−1) were designed using a 2-dimensional metal-organic framework and etching agent potassium chloride. Due to its high N content and large surface area, ultrafine Pd particles are uniformly distributed on the porous N-doped carbon support, which effectively enhances excellent reactivity and enables a TOF value of 2365 h−1 under additive-free conditions. The research also revealed that the strong interaction between Pd particles and pyridinic-N species can significantly slow metal agglomeration. Hence, the Pd/NCZIF-L (KCl) displayed good activity even after 10 cycling experiments, and it is a particularly competitive catalyst for hydrogen release from formic acid.