Ni-doped phenol resin was prepared with 1∶100 mass ratio of Ni(NO₃)₂·6H₂O to thermosetting phenol resin to optimize the structure and properties of pyrolytic carbon derived from phenol resin and increase its carbon yield. The specimens were cured at 200 ℃ and carbonized  under different atmospheres (carbon-embedded atmosphere and Ar atmosphere) and at different temperatures ( 600, 800, 1 000 and 1 200 ℃) for 3 h, respectively. The carbon yield was measured. Thermal decomposition characteristics of Ni-doped phenol resin, and the oxidation resistance, phase composition and microstructure of pyrolytic carbon were characterized by differential scanning calorimetry, X-ray diffraction, energy dispersive spectroscopy, scanning electron microscopy and transmission electron microscopy. The results show that the carbon yield of Ni+doped phenol resin carbonized at 800 or 1 000 ℃ is increased significantly, compared with that without any dopants. The graphitization degree of pyrolytic carbon structure derived from Ni-doped phenol resin increases with the increase of carbonization temperature. The massive multi-wall carbon nanotubes of 50-100 nm in diameter and of micrometre scale in length are generated at 1 000 ℃. Compared with the carbon-embedded atmosphere, carbon nanotubes can be more easily generated in Ar atmosphere, resulting in higher –carbon- yield and degree of crystallinity of the pyrolytic carbon derived from Ni-doped phenol resin. The oxidation resistance of the pyrolytic carbon derived from Ni-doped phenol resin at 1 200 ℃ is improved significantly and its highest oxidation temperature is increased by about 84 ℃, compared with that from Ni free phenol resin.