We describe the preparation of Prussian Blue films with several thicknesses, and their characterization by means of cyclic voltammetry and polarized reflection FTIR spectroscopy. The electrochemical experiments demonstrated a direct relationship between the film thickness and its intrinsic conductivity. The vibrational spectra showed asymmetrical bands in the vicinity of the cyanide stretching band. The s-polarization bands showed a shift to higher frequencies, while the p-polarization bands showed a downshift with increasing film thickness. The presence of shifted cyanide stretching bands in the s- and p-polarizations is attributed to the columnar shape of Prussian Blue grains formed in the growth process.