The invention discloses a preparation method for single-structure ferricyanide film monopolar pulse electro-deposition, which adopts a monopolar pulse electro-deposition method to prepare semi-conductive metal ferricyanide film on the surface of a conductive matrix, i.e. feeds a certain period of pulse deposition voltage and then controls the current to be zero within the interruption time to realize monopolar pulse, and prepares soluble or insoluble single-structure inorganic semi-conductive metal ferricyanide film by regulating the pulse voltage, pulse frequency, pulse make-break time (dutyratio) and other parameters in the solution containing potassium ferricyanide, transition metal salt and supporting electrolyte. The preparation method is simple and has strong operability; and the prepared single-structure metal ferricyanide film has excellent selectivity and sensitivity, and is the preferred material for the preparation of sensitive sensors and the electrical control ion separation technology.