The layered cobaltate Ca 3 Co 4 O 9 is of interest for energy-harvesting and heat-conversion applications because of its good thermoelectric properties and the fact that the raw materials Ca and Co are non-toxic, abundantly available, and inexpensive. While single-crystalline Ca 3 Co 4 O 9 exhibits high Seebeck coefficient and low resistivity, its widespread use is hampered by the fact that single crystals are too small and expensive. A promising alternative approach is the growth of highly textured and/or epitaxial Ca 3 Co 4 O 9 thin films with correspondingly anisotropic properties. Here, we present a two-step sputtering/annealing method for the formation of highly textured virtually phase-pure Ca 3 Co 4 O 9 thin films by reactive co-sputtering from Ca and Co targets followed by an annealing process at 730 °C under O 2 -gas flow. The thermally induced phase transformation mechanism was investigated by in-situ time-resolved annealing experiments using synchrotron-based 2D x-ray diffraction as well as ex-situ annealing experiments and standard lab-based x-ray diffraction. By tuning the proportion of initial CaO and CoO phases during film deposition, the method enables synthesis of Ca 3 Co 4 O 9 thin films as well as Ca x CoO 2 . With this method, we demonstrate production of epitaxial Ca 3 Co 4 O 9 thin films with in-plane electrical resistivity of 6.44 mΩcm and a Seebeck coefficient of 118 µVK -1 at 300 K.3