摘要： The ternary diamond-like compound Cu2SnSe3 is a potential thermoelectric material. Its Cu-Se conducting network leaves Sn as a likely doping site to optimize the carrier concentration without much deterioration to the carrier mobility. Thus, the precise determination on the intricate phase structures of Cu2SnSe3 is critical. Here, we first use the atomically resolved scanning transmission electron microscopy and reveal an unusual phase coexistence (monoclinic and orthorhombic phases) in Ag-doped Cu2SnSe3. Owing to coexisting phases and the orderedisorder transition in the orthorhombic phase, the Ag-doped Cu2SnSe3 shows an unusual three-stage behavior in its temperature-dependent electrical transport properties and achieves record high power factors in this system. The observed three-stage behavior due to the phase coexistence is supported by the first principle calculations, Hall measurements, and optical diffuse reflectance measurements. To fully understand the band structures and the coherent interface between these coexisting phases, a band contact model is proposed that could well explain the three-stage electrical transport behavior. Moreover, the phase coexistence is observed at the nanoscale regime, thus providing a high density of phase boundaries. Such coexisting nanophases play an important role in lowering the lattice thermal conductivity. As a result, the ZT value obtained in Cu2Sn0.93Ag0.07Se3 is double that of undoped Cu2SnSe3.