One of the ways to decrease thermal conductivity is nano structurization. Cobalt triantimonide (CoSb3) samples with added indium or tellurium were prepared by the direct fusion technique from high purity elements. Ingots were pulverized and re-compacted to form electrodes. Then, the pulsed plasma in liquid (PPL) method was applied. All materials were consolidated using rapid spark plasma sintering (SPS). For the analysis, methods such as X-ray diffraction (XRD), scanning electron microscopy (SEM) and scanning transmission electron microscopy (STEM) with a laser flash apparatus (LFA) were used. For density measurement, the Archimedes’ method was used. Electrical conductivity was measured using a standard four-wire method. The Seebeck coefficient was calculated to form measured Seebeck voltage in the sample placed in a temperature gradient. The preparation method allowed for obtaining CoSb3 nanomaterial with significantly lower thermal conductivity (10 Wm–1K–1 for pure CoSb3 and 3 Wm–1K–1 for the nanostructured sample in room temperature (RT)). The size of crystallites (from SEM observations) in the powders prepared was about 20 nm, joined into larger agglomerates. The Seebeck coefficient, α, was about –200μVK–1 in the case of both dopants, In and Te, in microsized material and about −400 μK−1 for the nanomaterial at RT. For pure CoSb3 , α was about 150 μVK−1 and it stood at −50 μVK−1 for nanomaterial at RT. In bulk nanomaterial samples, due to a decrease in electrical conductivity and inversion of the Seebeck coefficient, there was no increase in ZT values and the ZT for the nanosized material was below 0.02 in the measured temperature range, while for microsized In-doped sample it reached maximum ZT = 0.7 in (600K).