Chemical solution deposition as a simple method for preparation of oxide films is used to fabricate misfit structured Ca3Co4O9 thermoelectric films using cheap precursors, Ca and Co acetates, which opens up a simple route to fabricate large-area Co-based oxide thermoelectric films. The results show that when the annealing temperature is higher than 800 degrees C crystallized Ca3Co4O9 films can be obtained on single-crystal LaAlO3 substrates, whereas the Ca3Co4O9 films are amorphous for lower annealing temperatures. Experimental evidence shows that the amorphous Ca3Co4O9 films behave like semiconductors with enhanced resistivity and Seebeck coefficient within the measured temperature range. The magnetoresistance is positive indicating the absence of long-range order of the Co-ion spins. For the crystallized Ca3Co4O9 films, it can be seen that the thinner films show the characteristics of spontaneous dewetting induced by the stress, which suggests that it is possible to prepare nanostructured Ca3Co4O9 films through tailoring the film thickness and the lattice mismatch; whereas, for the thicker films the temperature dependence of the resistivity and the Seebeck coefficient shows that it is possible to prepare excellent Ca3Co4O9 thermoelectric films using chemical solution deposition route, which will broaden the range of preparation methods for misfit structured Co-based thermoelectric films.