Nb/Al2O3 and Nb/SiO2 as niobium carbide precursors were prepared from peroxoniobic acid (PNA). Alumina-supported niobium carbide and silica-supported niobium carbide were prepared by temperature programmed reaction (TPR) method under CH4–H2 mixed gas passage. Both catalysts were characterized by X-ray absorption fine structure (XAFS) and Raman spectroscopy. Nb/Al2O3 was more efficiently carburized than Nb/SiO2. The carbon deposition onto NbC occurred after the carburization completion of the Nb species.