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Cu3SbSe3-based composites have been prepared by self-propagating high-temperature synthesis (SHS) combined with spark plasma sintering (SPS) technology. Phase composition and microstructure analysis indicate that the obtained samples are mainly composed of Cu3SbSe3 phase and CuSbSe2/Cu2−xSe secondary phases. Our results show that the existence of Cu2−xSe phase can clearly enhance the electrical conductivity of the composites (~16 S/cm), which is 2.5 times higher than the pure phase. The thermal conductivity can remain at about 0.30 W·m−1·K−1 at 653 K. A maximum ZT (defined as ZT = S2σΤ/κ, where S, σ, Τ, κ are the Seebeck coefficient, electrical conductivity, absolute temperature and total thermal conductivity) of the sample SPS 633 can be 0.42 at 653 K, which is 60% higher than the previously reported values. Our results indicate that the composite structure is an effective method to enhance the performance of Cu3SbSe3.