Ti-based Bulk Metallic Glasses (BMGs) is expected to be used as new biomaterials. But, Ti-based BMGs have bioinertness. Coating the bioactive ceramics layers, such as titanate nanomesh layers, bioactivity of the Ti-base BMGs is improved. For more improving the bioactivity of the titanate nanomesh coated Ti-based BMGs, microstructures formation on the Ti-based BMGs by femtosecond laser irradiation might be effective. Ti-based BMGs, Ti-Zr-Cu-Pd, were irradiated with the femtosecond lasers. Various microstructures were formed on the Ti-based BMG's surface. By hydrothermal-electrochemical treatment, titanate nanomesh layers were created on the microstructures. After Simulated Body Fluid (SBF) immersion test, it was suggested that the bioactivity of the Ti-based BMG with microstrutures was more improved than bare Ti-based BMGs.