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Phenolic resin pyrolytic carbons were obtained by catalytic pyrolysis of phenolic resin at 500 °C, 600 °C, 700 °C, and 800 °C for 3 h in an argon atmosphere using copper nitrate as a catalyst precursor. The effects of copper salts on the pyrolysis process of phenolic resin as well as the structural evolution and oxidation resistance of phenolic resin pyrolytic carbons were studied. The results showed that copper oxide (CuO) generated from the thermal decomposition of copper nitrate was reduced to copper (Cu) by the gas generated from the thermal decomposition of the phenolic resin. Carbon nanofibers with tapered structures were synthesized by Cu catalysis of pyrolysis gas at 500–800 °C. The catalytic pyrolysis of phenolic resin with Cu increased the graphitization degree and reduced the pore volume of the phenolic resin pyrolytic carbons. The combined action improved the oxidation resistance of phenolic resin pyrolytic carbons. [ABSTRACT FROM AUTHOR]