Titanium implants with sufficient mechanical properties and biocompatibility have been in demand for rapid healing and successful surgery. Herein, porous Ti6Al4V scaffolds with multi-scale porosity were obtained by coupling dynamic freeze-casting with micro-arc oxidation (MAO). The fabricated scaffolds exhibited tailored pore sizes and interconnected pores. Compressive strength and elastic modulus were controlled by adjusting the porosity of the scaffolds. MAO was successfully conducted on the porous Ti6Al4V scaffolds by inhibiting gaseous emission from the electrolysis of water with the addition of ethanol to the MAO solution. Moreover, the biological response of preosteoblasts on the multi-scale porous Ti6Al4V scaffolds was enhanced owing to their porous topography and modified chemical composition.