Self-powered wearable electronics require thermoelectric materials simultaneously with a high dimensionless figure of merit (zT) and good flexibility to convert the heat discharged by the human body into electricity. Ag2(S,Se)-based semiconducting materials can well satisfy these requirements, and thus, they are attracting great attention in thermoelectric society recently. Ag2(S,Se) crystalizes in an orthorhombic structure or monoclinic structure, depending on the detailed S/Se atomic ratio, but the relationship between its crystalline structure and mechanical/thermoelectric performance is still unclear to date. In this study, a series of Ag2Se1‐xSx (x=0, 0.1, 0.2, 0.3, 0.4, and 0.45) samples were prepared and their mechanical and thermoelectric performance dependence on the crystalline structure was systematically investigated. x=0.3 in the Ag2Se1‐xSx system was found to be the transition boundary between orthorhombic and monoclinic structures. Mechanical property measurement shows that the orthorhombic Ag2Se1‐xSx samples are brittle while the monoclinic Ag2Se1‐xSx samples are ductile and flexible. In addition, the orthorhombic Ag2Se1‐xSx samples show better electrical transport performance and higher zT than the monoclinic samples under a comparable carrier concentration, most likely due to their weaker electron-phonon interactions. This study sheds light on the further development of flexible inorganic TE materials.