We report a novel hybrid material Na2Mo4O13/α-MoO3 as highly efficient catalytic wet air oxidation (CWAO) catalyst, which showed the highest ever activity at room temperature and atmosphere pressure for the degradation of cationic red GTL. SEM and TEM analyses indicated that this hybrid catalyst has bamboo-shaped nanofiber morphology. In view of practical applications, the influence of some key parameters including operation temperature, catalyst calcination temperature, and the volume of dye wastewater have been optimized. The mechanism for the superior catalytic performance was investigated. XRD, XPS, and ESR suggested the Na2Mo4O13/α-MoO3 hybrid catalyst possesses more O(2-) ions in the oxygen deficient regions than neat α-MoO3, promoting the formation of active ·OH radicals and resulting in a higher activity. Considering the facile preparation and its superior activity, this novel catalyst is promising for practical dye wastewater treatment.