Based on the oxygen evolving μ-oxido-Mn₄Ca cluster unit in photosynthesis II, Ca₂Mn₃O₈ films prepared by dip-coating and screen-printing were tested as oxygen evolving catalysts. Structural analysis confirmed that smooth 100 nm films can be grown from a Ca₂MnO₄ sol–gel solution showing a high orientation in (1 0 0) direction when deposited on F:SnO₂/quartz and quartz substrates. The distance found by X-ray diffraction between the layers exactly fitted the monoclinic layer compound of composition Ca₂Mn₃O₈. To compare the electrochemical behavior of this layer with the bulk Ca₂Mn₃O₈ powder, a 6 μm thick film was prepared by screen-printing. Differential electrochemical mass spectroscopy performed in 0.1 M KH₂PO₄ at pH 7 and 1 M Tris(hydroxymethyl)aminomethane at pH 7.8 revealed that both films were able to oxidize water as well as organic matter with a good correlation to the slope of the current density curves; however, the dip-coated films displayed lower current densities than the screen-printed Ca₂Mn₃O₈ layers. A closer look into the cyclic voltammetry revealed that capacity values were similar indicating that not only the different surface areas played a role, but variations in the specific capacity values possibly due to the orientation of the films or the manganese mixed valence in the surface as determined by X-ray photoelectron spectroscopy (XPS) could be responsible for these effects.