Abstract In the present study, the effect of nickel nitrate addition as a catalytic precursor for the in situ formation of Ni nanoparticles during the heating process has been investigated on the modification of microstructure and graphitization of amorphous carbon resulting from pyrolysis of phenolic resin. For this purpose, the prepared resin samples were cured in carbon substrate with and without additives at temperatures of 800, 1000, and 1250 °C. XRD, FESEM, and TEM studies were performed to investigate the phase and microstructural changes in the samples during the heating process. In addition to phase and microstructural studies, thermodynamic calculations of the reactions performed for the in situ formation of nickel nanoparticles and their effective factors during the curing process were performed. The results indicated that nickel nitrate is transformed to nickel nanoparticles of different sizes during the reduction process in a reduced atmosphere. The in situ formation of nickel nanoparticles and its catalytic effect led to the graphitization of carbon resulting from the pyrolysis of phenolic resin at a temperature of 800 °C and above. By increasing temperature, the morphology of the formed graphite changed and hollow carbon nanotubes, carbon cells, and onion skin carbon were formed in the microstructure. It was also observed that by increasing the temperature and the amount of additive, carbon nanotubes and their size are increased. A noteworthy point from thermodynamic calculations during the formation of nickel nanoparticles was that the nickel nanoparticles themselves acted as accelerators of nickel oxide reduction reactions and the formation of nickel nanoparticles. This increases the amount of amorphous carbon graphitization resulting from the pyrolysis of phenolic resin which leads to the formation of more carbon nanotubes at higher temperatures.