A series of Ca3-x Gd (x) Co4O9+delta precursor powders were synthesized by the polyacrylamide gel method, and their ceramics were obtained by the Spark Plasma Sintering (SPS). There were lots of defects in the sheet-like grains from SEM and TEM observations. The electrical and the thermal transport properties were obviously affected by the material microstructure. The small polaron hopping conduction mechanism was determined above 600 K, and the hopping activation energy increased with the increase of doping contents. It was found that the Seebeck coefficient and the resistivity of doped samples were markly enhanced due to the impurity compensation effect, and their thermal conductivities were decreased due to the defects scattering. The maximum figure of merit of ZT = 0.24 at 973 K was obtained for Ca2.7Gd0.3Co4O9+delta.