Shape memory alloys (SMAs) have been widely used as biomedical applications regarding their shape memory effect and superelasticity. In the past few years, Ti-Ni alloy (Nitinol) has been extensively investigated as an implant device due to its excellent biocompatibility, corrosion resistance, and suitable mechanical properties. However, in recent years, the concern about the use of Nitinol has become more serious related to the presence of Ni, which would lead to some physical problems, such as allergenic reactions. Hence, we devoted our research to the bio-functional nickel-free Ti-based shape memory alloys. According to the concept mentioned above, we dedicate ourselves to exploring the Ti-Zr-Nb alloy system and studying the microstructure evolution and the related mechanical properties associated with the composition variation. The accurate Ti-Zr-Nb content is verified by the electron probe microanalyzer (EPMA). The microstructure, martensitic transformation behavior, and shape memory effect of Ti-Zr-Nb alloys have been studied by X-ray diffraction (XRD), Optical Microscopy (OM), Scanning Electron Microscopy (SEM) observation, differential scanning calorimetry (DSC), and tensile test.