A GeNi alloy diffusion barrier for contacts on bismuth antimony telluride is proposed. Multiple gold contact diffusion barriers were tested at different thermal aging conditions in air and reducing atmospheres. Among all diffusion barriers, the GeNi alloy barrier shows the best performance for bulk samples with no substantial degradation of the contact resistance, no contact color change, and no change of thermoelectric properties. We observed DAu−GeNi = (9.8 ± 2.7) × 10−20 m2/s within the GeNi alloy barrier, which is 4 times smaller than DAu−BiSbTe. The presence of the initial Ge layer also proves to be effective in reducing nickel diffusion yielding DNi−BiSbTe = (8.57 ± 0.49) × 10−19 m2/s. During GeNi alloy formation, Ge diffusion into BiSbTe produces GeTe, which apparently blocks the van der Waals gaps eliminating Au and Ni fast diffusion pathways. Thermal aging of BiSbTe nanowires shows that Au and Ni diffusion degrades the thermoelectric power factor, whereas the GeNi alloy barrier sample is mostly preserved. The GeNi alloy barrier is a reliable solution to long-term thermal applications of BiTe-based materials.