Formic acid (FA) is considered as a new type of hydrogen storage material with great application prospect due to its high hydrogen content and easy recharging as a liquid. Seeking high efficiency catalysts to solve the problem of slow reaction kinetics of hydrogen evolution from FA is vital. In this work, polyethyleneimine modified graphene (PEI-rGO) was used as the catalyst substrate, and PEI-rGO supported AuPd nanocomposite material (Au_0.3Pd_0.7/PEI-rGO) was prepared by wet chemical method. The Au_0.3Pd_0.7/PEI-rGO catalyst exhibits remarkable activity for the hydrogen generation from FA, affording an unprecedented turnover frequency (TOF) of 2357.5 mol_H2∙ mol_catalyst^-1∙h ^-1 without any additives, which is superior to most heterogeneous catalysts under similar reaction conditions. Its excellent catalytic performance is attributed to the strong interaction between PEI-rGO substrate and AuPd nanoparticles, which regulates the size, dispersion and electronic structure of metal active components. Furthermore, the recycle test result shows that the catalyst has good stability.