A two-step synthesis approach was utilized to grow CaMnO3 on M-, R- and C-plane sapphire substrates. Radio-frequency reactive magnetron sputtering was used to grow rock-salt-structured (Ca, Mn)O followed by a 3-h annealing step at 800 °C in oxygen flow to form the distorted perovskite phase CaMnO3. The effect of temperature in the post-annealing step was investigated using x-ray diffraction. The phase transformation to CaMnO3 started at 450 °C and was completed at 550 °C. Films grown on R- and C-plane sapphire showed similar structure with a mixed orientation, whereas the film grown on M-plane sapphire was epitaxially grown with an out-of-plane orientation in the  direction. The thermoelectric characterization showed that the film grown on M-plane sapphire has about 3.5 times lower resistivity compared to the other films with a resistivity of 0.077 Ωcm at 500 °C. The difference in resistivity is a result from difference in crystal structure, single orientation for M-plane sapphire compared to mixed for R- and C-plane sapphire. The highest absolute Seebeck coefficient value is − 350 µV K−1 for all films and is decreasing with temperature.