A method for determining the relative content of nickel hexacyanoferrate insoluble and soluble structures. According to the method, by the adoption of a three-electrodes system and a potentiostatic instrument, a film electrode precipitated with an electroactive nickel hexacyanoferrate semiconductor film is used as a working electrode to respectively determine the cyclic voltammetry curve of the electrode in a sylvite-containing solution, and different peak shape characteristics of the cyclic voltammetry curve generated during an oxidation and reduction process of the nickel hexacyanoferrate film electrode with different structures are utilized to determine the relative content of the insoluble and soluble structures. The method provided by the invention is simple, is fast and convenient to operate, and has good reliability.