Nanostructured niobium oxides were synthesized by hydrothermal treatment. Oxalic acid or H2O2 as structure-directing agents resulted in materials with different properties. These new catalysts demonstrated great performance in decomposition of methylene blue (MB). The best result for Fenton-like reactions indicated the removal of 80% of MB in just 30 min using the Nb2O5-HP. The photocatalysis tests using UV light irradiation provided the removal of up to 86% of MB after 5 h using the Nb2O5-OX catalyst.