The invention provides a three-layer film four-chamber aqueous solution plate-and-frame electrolytic cell and application thereof, belongs to the field of electrochemical industries, and aims to solve the problem about recycling of chromium-containing wastewater and to improve the time-space yield of the electrolytic cell for sufficient utilization of the electric energy. The electrolytic cell comprises a cathode chamber, a salt chamber, an acid chamber and an anode chamber which are sequentially arranged and connected together, wherein a cationic film I is arranged between the cathode chamber and the salt chamber; a cationic film II is arranged between the acid chamber and the anode chamber; an anionic film is arranged between the salt chamber and the acid chamber; the anode chamber contains a sulfuric acid solution of chromium sulfate; the acid chamber contains a sulfuric acid solution; the salt chamber contains sodium sulfate or a potassium sulfate solution; the cathode chamber contains sodium hydroxide or a potassium hydroxide solution; and electrolytes in all the chambers flow in a down-in and up-out manner and are forcibly circulated by matched corrosion-resistant circulating pumps. By utilization of the electrolytic cell provided by the invention, the anodic current efficiency reaches 65-75%, the cathodic current efficiency reaches 80-90%, the total current efficiency reaches 145-165%, and the time-space yield of the electrolytic cell is greatly improved.