The interfacial microstructure and joining properties of Titanium-Zirconium-Molybdenum (TZM) alloy joints were characterized by SEM, EDS, XRD and mechanical tests, etc. The results showed that the Ni-Ti brazing filler metal can efficiently realize high-temperature vacuum brazing of TZM. The formation MoNi₄ phase from Mo of the base metal and Ni in the braze metal was the main reason for the metallurgical bond between the TZM and the Ni-13.7Ti / TZM interface region. Ti in Ni-44Ti braze metal dissolved in Mo to form an infinite solid solution in TZM / Ni-44Ti / TZM interface zone, forming a metallurgical bond between the braze metal and TZM. However, a serious inter-granular infiltration phenomenon was observed when Ni-44Ti braze alloy was used to braze TZM alloy. The degree of inter-granular infiltration and corrosion of the base material significantly reduced with a decrease of Ti content in the braze alloy. The average shear strength of TZM / Ni-13.7Ti / TZM brazed joints reached 193 MPa, while the average shear strength of TZM/Ni-44Ti/TZM brazed joints reached 167 MPa. The lower shear strength of TZM/Ni-44Ti/TZM was attributed to the inter-granular infiltration due to the higher content of Ti in the brazing filler.