The structure and electronic transport properties of polymer-derived pristine and boron-doped silicon carbonitride ceramics have been studied, with particular emphasis on understanding the effect of annealing treatments. Structural analysis using the radial distribution function formalism showed that the local structure is comprised of basic building blocks of Si tetrahedra with B, C, and N at the corners. Comparison of the electrical properties of pristine and boron-doped ceramics shows that boron doping leads to enhanced p-type conductivity, with a small positive thermopower. The postpyrolysis annealing treatments at elevated temperatures have a significant effect on the conductivity. The conductivity variation with temperature for these ceramics shows Mott's variable range hopping (VRH) behavior, characteristic of a highly defective semiconductor.