Reduced energy consumption and environmentally friendly, abundant constituents are gaining more attention for the synthesis of energy materials. A rapid, highly scalable, and process-temperature-sensitive solution synthesis route is demonstrated for the fabrication of thermoelectric (TE) Cu2-xSe. The process relies on readily available precursors and microwave-assisted thermolysis, which is sensitive to reaction conditions; yielding Cu1.8Se at 200 degrees C and Cu2Se at 250 degrees C within 6-8 min reaction time. Transmission electron microscopy (TEM) revealed crystalline nature of as-made particles with irregular truncated morphology, which exhibit a high phase purity as identified by X-ray powder diffraction (XRPD) analysis. Temperature-dependent transport properties were characterized via electrical conductivity, Seebeck coefficient, and thermal diffusivity measurements. Subsequent to spark plasma sintering, pure Cu1.8Se exhibited highly compacted and oriented grains that were similar in size in comparison to Cu2Se, which led to its high electrical and low thermal conductivity, reaching a very high power-factor (24 mu W/K(-2)cm(-1)). Density-of-states (DOS) calculations confirm the observed trends in electronic properties of the material, where Cu-deficient phase exhibits metallic character. The TE figure of merit (ZT) was estimated for the materials, demonstrating an unprecedentedly high ZT at 875 K of 2.1 for Cu1.8Se sample, followed by 1.9 for Cu2Se. Synthetic and processing methods presented in this work enable large-scale production of TE materials and components for niche applications.