Ca 3 Co 4 O 9 thermoelectric materials in form of thick films are very promising in practical applications due to their low costs and relatively high performance. In this work, two different suspensions have been used to produce different coatings on Al 2 O 3 polycrystalline substrates with theoretical green thickness of 360 and 2000 µm. Moreover, the effect of substrate has also been investigated using Al 2 O 3 monocrystalline substrates and a 360 µm green thickness. Sintering procedure at 900 ºC for 24 h has drastically decreased coating thickness. XRD performed on the coatings surface has shown the formation of small amounts of Ca 3 Co 2 O 6 secondary phase on the polycrystalline substrates, while it was more abundant, and accompanied by Ca 2 Co 2 O 5 on the monocrystalline substrates. In spite of the higher secondary phases content, monocrystalline substrates produced a slight grain orientation which led to the highest thermoelectric properties between the samples (0.38 mW/K 2 m at 800 ºC), and very close to the best reported values in the literature.