We report a simple thermal decomposition method to prepare Nb2O5-modified Nb3O7F hybrid photocatalysts for the first time. The crystallographic phase sensitively correlates with heat-treated temperature. Nb3O7F/Nb2O5 nanocomposites exhibit enhanced photocatalytic performance compared to bare Nb3O7F. The enhanced photocatalytic activity can be attributed to perfect crystallization and synergistic effect.