All-solid-state thin-film secondary cells were prepared using transition metal hexacyanometallates as anode and cathode materials. Two different approaches were employed to prepare highly stable films of the electroactive materials viz. using aluminum substrate as current collector and deposition under centrifugal forces. At the first stage, the cell design was examined for a well-known case, Prussian blue (PB) secondary cell. The experimental results were indicative of the fact that the cell properties such as its charge/discharge behavior, specific capacity, cyclability, and coulombic efficiency are significantly improved. At the second state, the cell design proposed was successfully used to fabricate a high-voltage secondary cell based on chromium hexacyanochromate (CrHCC) anode and Prussian blue (PB) cathode. Then, eight unit cells were connected in series to prepare a rechargeable battery with an operating voltage of ca. 20V. Thus, the results are of interest for the preparation of microbatteries with specified properties.