Nano-sized Ca3Co(4-x)Mn(x)O9 (0 < or = x < or = 0.6) thermoelectric powders were synthesized by solution combustion method, using aspartic acid as fuel. The microstructure and high-temperature (500-800 degrees C) thermoelectric properties of the Ca3Co(4-x)Mn(x)O9 were investigated. The addition of Mn for Co in Ca3Co(4-x)Mn(x)O9 resulted in a decrease of the electrical conductivity and a significant increase of the Seebeck coefficient. Consequently, the power factor was remarkably enhanced by the addition of Mn. Ca3Co(3.7)Mn(0.3)O9 sample showed the highest value of the power factor (1.24 x 10(-4) Wm(-1) K(-2)) at 800 degrees C. We believe that the Ca3Co(4-x)Mn(x)O9 is strongly desirable as a novel high-temperature thermoelectric material for power generation.