Catalytic dehydrogenation of formic acid (FA) is one strategy to generate hydrogen from an easily handled chemical and meet the clean-energy demand simultaneously. The Pd/N-doped carbon catalyst is famous for boosting the activity of active metal in FA dehydrogenation. However, the origin of achieving highly catalytic activity remains controversial. Herein, a variety of Pd/N-doped carbon catalysts were systematically prepared by regulating different N doping content and reduction conditions (H2 and NaBH4) for promoting hydrogen production from FA under ambient conditions without additives. The results showed that N dopants have a great impact on the electronic state and particle size of Pd. Moreover, the electronic state of Pd is also sensitive to the reduction methods. The catalyst with the highest pyridinic-N content presented the best catalytic performance after being reduced in H2 flow at 260 °C, and its initial TOF value is 2656 h−1 without additives at 50 °C. The electronic levels investigation of the active metal can provide new ideas for the design of highly efficient catalysts for FA dehydrogenation.