In this chapter, porous nanocrystalline bioalloys Ti-6Al-4V, Ti-15Zr-4Nb, and Ti-6Zr4Nb formation is described. The alloys were prepared by mechanical alloying (MA) followed by pressing, sintering, and subsequent anodic electrochemical etching in 1M H3PO4 + 2% HF electrolyte at 10 V for time of 30-300 min. We show that, ultrafine structure improves etching process. The electrolyte penetrates sinters through the empty spaces and the grain boundaries, resulting in effective grains removing and pores-formation. The porosity of the Ti-15Zr-4Nb is larger than the Ti-6Al-4V. The macropore diameter reaches up to 60 μm, while the average micropore size is in the range from 3.5 to 5.46 nm for Ti-15Zr-4Nb and Ti-6Al-4V electrochemically etched alloys, respectively.