Ultrafine and highly dispersed PdAu nanoparticles were immobilized on amine functionalized carbon black (VXC-72-NH₂) for dehydrogenation of formic acid (FA). The introduction of amines is of vital importance for the formation of ultrafine PdAu nanoparticles (∼1.5 nm). Moreover, the presence of the amino groups also increased the electron density of PdAu nanoparticles, and this effect facilitated the formation of metal-formate, which further enhanced the rate of the catalytic dehydrogenation of FA. The as-prepared Pd_0.6Au_0.4/VXC-72-NH₂ exhibited high catalytic activity and 100% H₂ selectivity for dehydrogenation of formic acid without any additive, with turnover frequency (TOF) values of 7385 h⁻¹ at 298 K and 17 724 h⁻¹ at 333 K, which are the highest TOF values ever reported among heterogeneous catalysts for FA dehydrogenation.