Abstract: The preparation of thermocouple is the core link of thermoelectric technology theory into application. The high-temperature end electrode connector of thermocouple of silicon-germanium alloy is designed and prepared. First, W-MoSi₂-Si₈₀Ge₂₀ was prepared by one-step hot pressing method, and then W-W was soldered with BNi5 solder to prepare W-BNi5-W-MoSi₂-Si₈₀Ge₂₀ high-temperature end multilayer electrode connector. The electrode joint was subjected to a high-temperature accelerated experiment at 900 ℃for 100h. The contact resistance and shear strength of the electrode joint before and after the high temperature acceleration experiment were tested. SEM and EDS were used to analyze the interface morphology and element distribution of the electrode joints before and after the high temperature acceleration experiment. The results show that the prepared multi-layer electrode joint has better connection effect. The contact resistance of the joint after connection is 0.29mΩ · cm², the shear strength is 15.6MPa, and the joint performance deteriorates after the high temperature acceleration test. SEM and EDS analysis show that the difference between the thermal expansion coefficients of solder and W at the W-BNi5-W interface leads to a gap between the interfaces, which is the main reason for the deterioration of the joint performance. MoSi₂ can effectively block the diffusion of elements between W and Si₈₀Ge₂₀, which is conducive to maintaining the thermoelectric performance of silicon-germanium alloy.