The invention discloses a method for preparing a composite film photoelectrode, and the method comprises the following steps of: preparing an electrode matrix: taking platinum-plated titanium conductive glass as an electrode substrate, soaking the electrode substrate in a hydrogen peroxide solution, washing the electrode substrate with water, and performing ultrasonic treatment to form a film electrode layer; then, putting the film electrode layer into a sodium hydroxide solution for ultrasonic treatment, repeatedly carrying out ultrasonic cleaning by using deionized water, and then, drying; finally, electropolishing and ultrasonically washing with water in a sodium hypochlorite electrolytic cell to prepare the electrode matrix, and drying the electrode matrix; and pretreating the electrode matrix: adding graphene into a mixed solution of sodium carboxymethylcellulose and styrene to obtain a coating solution; performing coating solution spin-coating on the electrode matrix, and performing annealing treatment to obtain an electrode preform; and preparing a composite film photoelectrode: preparing an LDH electrode from the electrode preform by using an electro-deposition method, placing the prepared LDH electrode in a muffle furnace, and calcining and air-cooling to prepare an MMO electrode; and preparing an MMO photoelectrode covered by a lead dioxide film by using an electrodeposition method, washing with water, and drying.