The Ba-, La- and Ag-doped polycrystalline Ca2.9M0.1Co4O9 (M=Ca, Ba, La, Ag) thermoelectric bulk samples were prepared via citrate acid sol-gel synthesis method followed by spark plasma sintering technique. The bulk samples were characterized and analyzed with regard to their phase compositions, grain orientations as well as microstructures. The high temperature thermoelectric transport properties of the bulk samples were studied in detail. All bulk samples were found to be single-phased with modified body texture. The electrical resistivity was modulated as a result of carrier concentration modification, however the carrier transport process was not influenced; the Seebeck coefficient was deteriorated simultaneously. The total thermal conductivity was remarkably reduced, on account of the decreasing of phonon thermal conductivity. The thermoelectric properties of the Ba-, La-, and Ag-doped bulk samples were optimized, and the Ba-doped Ca2.9Ba0.1Co4O9 system was found to have the highest dimensionless figure of merit ZT0.20 at 973K, which was remarkably higher than that of the un-doped sample. The Ba-, La- and Ag-doped polycrystalline Ca2.9M0.1Co4O9 (M = Ca, Ba, La, Ag) thermoelectric bulk samples were prepared via citrate acid sol-gel synthesis method followed by spark plasma sintering technique. The bulk samples were characterized and analyzed with regard to their phase compositions, grain orientations as well as microstructures. The high temperature thermoelectric transport properties of the bulk samples were studied in detail. All bulk samples were found to be single-phased with modified body texture. resistivity was modulated as a result of carrier concentration modification, however the carrier transport process was not influenced; the Seebeck coefficient was deterbly modified, on account of the decreasing of phonon thermal conductivity. The thermoelectric properties of the Ba-, La-, and Ag-doped bulk samples were optimized, and the Ba-doped Ca2.9Ba0.1Co4O9 system was found to have the highes t dimensionless figure of merit ZT0.20 at 973K, which was remarkably higher than that of the un-doped sample.