Pyrolysis of methane is a carbon-economic method to obtain valuable carbon materials and COx- free H2, under the carbon peaking and carbon neutrality goals. In this work, we propose a methane pyrolysis process to produce graphite and H2 using bubble column reactor containing NiO/Al2O3 and NaCl–KCl (molten salt). The process was optimized by the different amounts of NaCl–KCl, the CH4/ Ar ratio and temperature, indicating that the CH4 conversation rate could reach 92% at 900 °C. Meanwhile, we found that the addition of molten salt could obtain pure carbon materials, even if the conversation rate of CH4 decreases. The analysis of the carbon products revealed that graphite could be obtained.