B4C ceramics doped with various content of Si (0 to 2.03 at%) are prepared via hot pressing. The composition and microstructure of the ceramics are characterized by means of XRD and EPMA. Their electrical conductivity and Seebeck coefficient of the samples are measured from room temperature up to 1500K. The electrical conductivity increases with temperature, and more rapidly after 1300K; the Seebeck coefficient of the ceramics also increases with temperature and rises to a value of about 320μVK−1. The value of the figure of merit of Si-doped B4C rises to about 4 × 10−4K−1 at 1500K.