Single-crystalline tin-selenide (SnSe) has emerged as a high-performance and eco-friendly alternative to the lead-chalcogens often used in mid-temperature thermoelectric (TE) generators. At high temperature >800 K, the phase transition from Pnma to Cmcm causes a significant rise in the TE figure-of-merit (zT) curve. Conversely, the SnSe TE requires a booster at low temperatures, which allows broader applicability from a device perspective. Herein, a synergy of Cu alloy and Ag-coating is realized through a sequential multi-step synthesis, designed to combine different metal deposition effects. Single-crystalline (Cu2Se)x(SnSe)1−x alloys grown by the Bridgman method were then coated with a thin Ag layer by radio frequency (RF) sputtering, and the interlayer epitaxial film was observed via electric-current assisted sintering (ECAS). Consequently, the thin Ag-coating improves the electrical conductivity (σ) and reduces the thermal conductivity (κ) for (Cu2Se)0.005(SnSe)0.995+Ag alloy, increasing the zT curve at close to room temperature (373 K). The incorporation of multistep addition by ECAS enables tuning of the overall solubility of the alloy, which opens a new avenue to optimize TE performance in anisotropic 2D materials.