Highly efficient dehydrogenation of formic acid (FA) at room temperature is a safe and suitable way to obtain hydrogen and promote the development of hydrogen storage application. Herein, the phosphorous-alloyed Pd nanoclusters loading on nitrogen-doped carbon (PdP/NC) were prepared and recognized as the highly active nanocatalysts for the dehydrogenation of FA. The PdP/NCs with controlled sizes and compositions were prepared by an easy self-limiting synthesis in an aqueous solution. The best PdP/NC exhibited a remarkable catalytic activity with a high turnover frequency of ∼3253.0 h-1 than the compared nanocatalysts for the dehydrogenation of FA at room temperature. The catalytic kinetics and durability studies showed that both the alloyed P in Pd crystals and doped N in the carbon support could effectively tailor the electronic states of the Pd surface and further optimize the adsorption energy of FA. Based on the Sabatier principle, the proper adsorption energy accelerated the dehydrogenation reaction and correspondingly enhanced the activity and durability. The work proposed a high-efficiency nanocatalyst for safe hydrogen generation and may be extended to create other similar nanocatalysts with different compositions and nanostructures.