The invention relates to novel modified phenol-formaldehyde resin, and preparation of modified phenol-formaldehyde/epoxy resin anticorrosion coating by utilization of the modified phenol-formaldehyde resin and epoxy resin. Aiming at characteristics of traditional phenol-formaldehyde resin raw materials, high toxicity, high volatility, high irritation, and the like of formaldehyde, alpha, beta-furylacrolein which is high in boiling point, low in volatility and low in toxicity in place of formaldehyde is adopted to synthesize the modified phenol-formaldehyde resin with phenol, a furan ring and a flexible side chain are introduced into the modified phenol-formaldehyde resin, furan resin is formed and system brittleness is improved. The modified phenol-formaldehyde resin can be widely applied to the fields of plastic, glass fiber reinforced plastic, amine mud, amine adhesives, coating and the like. The modified phenol-formaldehyde/epoxy resin anticorrosion coating is prepared from the modified phenol-formaldehyde resin and the epoxy resin, has excellent properties of the epoxy resin and the furan resin, such as high adhesion force, acid resistance, alkali resistance, resistance to high temperature and ageing resistance, and can be used as coating for boats, oil tanks, pipes, and other structural objects.