The highly electrically conductive graphene papers prepared from graphene oxide have shown promising perspectives in flexible electronics, electromagnetic interference (EMI) shielding, and electrodes. To achieve high electrical conductivity, the graphene oxide precursor usually needs to be graphitized at extremely high temperature (~ 2,800 °C), which severely increases the energy consumption and production costs. Here, we report an efficient catalytic graphitization approach to fabricate highly conductive graphene papers at lower annealing temperature. The graphene papers with boron catalyst annealed at 2,000 °C show a high conductivity of ~ 3,400 S·cm^–1, about 47% higher than pure graphene papers. Boron catalyst facilitates the recovery of structural defects and improves the degree of graphitization by 80%. We further study the catalytic effect of boron on the graphitization behavior of graphene oxide. The results show that the activation energy of the catalytic graphitization process is as low as 80.1 kJ·mol^–1 in the temperature ranges studied. This effective strategy of catalytic graphitization should also be helpful in the fabrication of other kinds of highly conductive graphene macroscopic materials.