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Metallic barrier layer is a key component in thermoelectric (TE) devices, but it is rarely investigated for the recently discovered inorganic ductile TE materials. In this work, we demonstrate that tungsten (W) is the excellent metallic barrier layer for Ag2S1−xSex ductile thermoelectric materials. The phase composition, microstructure, adhesive strength, and interfacial contact resistivity (ρC) of the W/Ag2S1−xSex joint have been systematically investigated. The sputtered W film has high adhesive strength and little interdiffusion/reaction with Ag2S1−xSex. The ρC decreases with increasing the Se content, which can be understood by the Thermionic-field Emission model. This work would guide the development of high-performance flexible TE devices based on ductile TE materials. [ABSTRACT FROM AUTHOR]