In modern age, much thermal energy is emitted from ceramic and/or steel industries. Their temperature range is between 500 K and 1300 K. Thermoelectric materials are promising to utilize the waste heat, because of no CO2 emission and long life due to no moving parts. The thermoelectric properties of every thermoelectric material have temperature dependence and high performance appears at a specific temperature range. If the proper materials are placed and joined along the temperature gradient to form an FGM, the performance should be higher than a monolithic material. The performance of a thermoelectric material is expressed by the dimensionless figure of merit ZT=α2ρ-1κ -1T, where α is the Seebeck coefficient, ρ is the electrical resistivity, κ is the thermal conductivity, and T is absolute temperature. Thermoelectric oxides are suitable for high temperature materials because of chemical stability. NaxCoO2 shows relatively high ZT value in thermoelectric oxide at the temperature range below 800 K. Ca3Co4O9 shows ZT ~1 at 1000 K. Recently, it is reported that Ca3Co2O6 that is formed by decomposition of Ca3Co4O9 at 1173 K has high performance at 1300 K. The properties and fabrication condition of high density Ca3Co2O6 are, however, not reported in detail. In order to improve the thermoelectric properties and to shift the temperature range for Ca3Co2O6, we investigated the effects of element substitution. In this experiment, the sintered Ca3Co2-xMxO6 (x=0 or 0.2, M= Mn, Mo or V) were prepared by solid-state reaction or hot pressing. Relative density of Ca3Co2O6 by hot-pressing (HP) was over 94% which is larger than one of Ca3Co2O6 by solid-state reaction (SSR). The resistivity of Mo- or V-substituted Ca3Co2O6 (HP-Mo or HP-V) were lower than one of non-substituted Ca3Co2O6 (HP). The resistivity of Mo-substituted Ca3Co2O6 (HP-Mo) showed the lowest value of 4.3×10-2 Ωcm in all specimens at 1181 K. The power factor α2ρ-1 of Ca3Co2O6 (HP-Mo) was 64.2 Wm-1K-2, which is the largest of all specimens at 1178 K, and this value is approximately 1.3 times higher than 48.8 Wm-1K-2 for Ca3Co2O6 (HP).