A Bi2Te3/Bi2S3@Bi nanocomposite with a network microstructure was successfully synthesized via a hydrothermal method and spark plasma sintering. This composite was constructed from Bi2Te3 nanoparticles and Bi2S3@Bi nanowires, and its network structure is beneficial for obtaining excellent thermoelectric performance. A ZT peak of 1.2 at 450 K was realized for the nanocomposite sample.