Abstract: Reduced graphene oxide and graphene oxide (rGO, GO) were synthesised from carbon nanofibers, which were formed in catalytic thermal decomposition of methane (CDM) and biogas with different catalysts used in the process. The aim of the work was valorization of CDM carbon nanofiber products. The samples were characterized using Raman spectra, a scanning electron microscope and a transmission electron microscope. As a result, we observe exfoliation and the sample surface to obtain the best samples of rGO and GO. These valuable products will be useful in improving the methane/biogas thermal decomposition process. The samples have been compared and a single layer of reduced graphene oxide can be seen on images. In addition, the influence of various catalysts (especially for Fe/Al2O3 and Ni/Al2O3) used in CDM on quality of samples was compared.