To improve the pyrolytic carbon (PyC) deposition rate of Carbon/Carbon (C/C) composites prepared by the traditional chemical vapor infiltration (CVI) method, the 3D Ni/wood-carbon (3D Ni/C) catalyst was introduced into the CVI process. The effects of catalyst on the density of C/C composites were studied, and the deposition rate and morphologies of PyC were investigated after catalytic CVI. The morphologies of catalyst and PyC were characterized by scanning electron microscope and polarized light microscopy. The catalytic deposition mechanism of PyC was studied by density functional theory. The experimental results show that the initial carbon deposition efficiency of the catalytic pyrolysis process was 3–4 times that of the noncatalytic process. The catalyst reduced the energy barrier in the first step of deposition reaction from 382.55 to 171.67 kJ/mol according to simulation results. The pyrolysis reaction energy with Ni catalyst is reduced by 54% than that without the catalyst.