The thermal stability of joints in thermoelectric (TE) modules, which are degraded during interdiffusion between the TE material and the contacting metal, needs to be addressed in order to utilize TE technology for competitive, sustainable energy applications. Herein, we deposit a 200 nm-thick Zr-based thin-film metallic glass (TFMG), which acts as an effective diffusion barrier layer with low electrical contact resistivity, on a high-zT Se-doped AgSbTe 2 substrate. The reaction couples structured with TFMG/TE are annealed at 673 K for 8-360 hours and analyzed by electron microscopy. No observable IMCs (intermetallic compounds) are formed at the TFMG/TE interface, suggesting the effective inhibition of atomic diffusion that may be attributed to the grain-boundary-free structure of TFMG. The minor amount of Se acts as a tracer species, and a homogeneous Se-rich region is found nearing the TFMG/TE interface, which guarantees satisfactory bonding at the joint. The diffusion of Se, which has the smallest atomic volume of all the elements from the TE substrate, is found to follow Fick's second law. The calculated diffusivity (D) of Se in TFMG falls in the range of D∼10-20 -10-23 (m 2 /s), which is 106 ∼107 and 1012 ∼10 13 times smaller than those of Ni [10-14 -10 -17 (m2 /s)] and Cu [10 -8 -10 -11 (m 2 /s)] in Bi2 Te3, respectively.