In this study, the boron-doped barium-stabilized bismuth cobalt oxide thermoelectric nanocrystalline ceramic powders were produced by the polymeric precursor technique. The powders were characterized by X-ray diffraction, scanning electron microscopy, and the physical properties measurement system. The X-ray diffraction results showed that these patterns have mixture of two phases as face-centered cubic and body-centered cubic. Values of the crystallite size, the dislocation density, and the microstrain were calculated by the Scherrer equation. According to these values, the crystallite size decreased from 60 to 51 nm with the boron addition in the boron-undoped and boron-doped samples, respectively. The scanning electron microscope results showed that nanograins are rarely seen in the boron-undoped samples, but nanograins turn into needle-like and layered structures with boron addition. The diameters distribution of nanofibers was calculated. The average diameter of the boron-doped sample is smaller than the boron-undoped sample. The physical properties measurement system values showed that the electrical and thermal conductivity, the Seebeck coefficient, and the figure of merit increased with the temperature rise for both samples. The boron-doping effect increased the electrical and thermal conductivity, decreased the Seebeck coefficient, and decreased the figure of merit.