The invention discloses an anti-corrosive coating for aluminum electrolytic cells and a preparation method thereof. The anti-corrosive coating comprises the following components: polycarbonate, phenolic resin, barium stearate, a defoaming agent, 2-ethyl cyanoacrylate, ethylene-glycol-dimethacrylate, hexamine, carboxymethylcellulose, polyethylene glycol, polyvinylformal acetal, and polybor-organosiloxane. The preparation method comprises the following steps: uniformly mixing polycarbonate, phenolic resin, barium stearate, 2-ethyl cyanoacrylate, ethylene-glycol-dimethacrylate, carboxymethylcellulose and polyethylene glycol, adding the obtained mixture into a reaction kettle, heating for reacting under the condition of inert gas protection, cooling to 40-50 DEG C, adding a defoaming agent, hexamine and polyvinyl formal acetal, continuing to stir so as to obtain a mixture 2; and adding polybor-organosiloxane in the mixture 2, heating for reacting under vacuum conditions, and cooling to room temperature, so that the anti-corrosive coating is obtained. The anti-corrosive coating provided by the invention is excellent in properties and suitable for use.