Perovskite-type CaMnt-xNbxO3 +/-delta (x = 0.02, 0.05, and 0.08) compounds were synthesized by applying both a "chimie douce" (SC) synthesis and a classical solid state reaction (SSR) method. The crystallographic parameters of the resulting phases were determined from X-ray, electron, and neutron diffraction data. The manganese oxidations states (Mn4+/Mn3+) were investigated by X-ray photoemission spectroscopy. The orthorhombic CaMn1-x,NbxO3 +/-delta (x = 0.02, 0.05, and 0.08) phases were studied in terms of their high-temperature thermoelectric properties (Seebeck coefficient, electrical resistivity, and thermal conductivity). Differences in electrical transport and thermal properties can be correlated with different microstructures obtained by the two synthesis methods. In the high-temperature range, the electron-doped manganate phases exhibit large absolute Seebeck coefficient and low electrical resistivity values, resulting in a high power factor, PF (e.g., for x = 0.05, S1000K = -180 mu V K-1, rho(1000K) = 16.8 m Omega cm, and PF > 1.90 x 10(-4) W m(-1) K-2 for 450 K < T < 1070 K). Furthermore, lower thermal conductivity values are achieved for the SC-derived phases (K < 1 W m(-1) K-1) compared to the SSR compounds. High power factors combined with low thermal conductivity (leading to ZT values > 0.3) make these phases the best perovskitic candidates as n-type polycrystalline thermoelectric materials operating in air at high temperatures.