The fabrication of nanoporous anatase TiO2 on a microstructured Ti base is achieved through an innovative hybrid fabrication method involving femtosecond laser ablation coupled with H2O2 oxidation and annealing. The anatase TiO2 micro-nanostructures have superior photocatalytic degradation of methyl orange due to enhanced light harvesting capacity and surface area. The photodegradation efficiency increases by a maximum of 80% compared to the nanoporous anatase TiO2 fabricated through H2O2 oxidation and annealing only (without femtosecond laser ablation). Meanwhile, The anatase TiO2 micro-nanostructures show good cyclic performance, indicating a great potential for practical application. The proposed hybrid method can easily tune the morphology and size of microstructure by simply adjusting the femtosecond laser parameters, showing advantage in fabricating of micro-nanostructures with a rich variety of morphologies.