Abstract: Single-phaseβ-Zn₄Sb₃ was synthesized by a method of vacuum melting. TiO₂/β-Zn₄Sb₃ composite materials were obtained by hydrolyzing the tetrabutyltitanatein alcohol solution. A SPS method was conducted to achieve dense bulk samples. The influence of TiO₂ contents on thermoelectric properties of the composites was studied. Experimental results showed that with the increase of the TiO₂ contents, the Seebeck value increased, while the electrical conductivity and the thermal conductivity significantly decreased. At 638 K, the Z_T value reached 0.68, which was 19% higher than that of pureβ-Zn₄Sb₃.