The development of a highly efficient non-noble catalyst for rapid releasing of hydrogen from methanol/water at low temperature is urgent, but challenge. In this paper, the high content of graphited N-doped carbon encapsulated reducing state copper catalyst was fabricated for low-temperature aqueous reforming of methanol. The Cu@NGC-600 catalyst gives excellent hydrogen production rate of 46.15 μmol·gcat-1·s-1 at 190 °C, which is 4 times higher than the commercial 20 % Pt/C catalyst and 3 times higher than other reported Cu-based catalysts (such as the Cu@NC-200 catalyst). Characterization and DFT calculation results revealed that rich doping of graphite N and the synergistic effect of Cu–N strengthened the electron transfer between copper and the NC matrix, decrease the reduction temperature of catalyst, which enabled the Cu to maintain a highly reduced state of Cu0/Cu+ during APRM for low temperature (150–190 °C) hydrogen production.