The thin film metallic glass (TFMG) is an effective diffusion barrier layer for PbTe-based thermoelectric (TE) modules. Reaction couples structured with Cu/TFMG/PbTe are prepared via sputter-deposition and are annealed at 673 K for 8-96 h. The transmission line method is adopted for the assessment of electrical contact resistivity upon the PbTe/TFMG, and the value remains in the range of 3.3-2.5 × 10−9 (Ω m2). The titanium-based TFMG remains amorphous upon annealing at 673 K for 48 h and effectively blocks the inter-diffusion by not having grain-boundaries, which only allows the bulk diffusion between the metal electrode and the TE substrate.