The invention discloses a polyurethane/polyurea composite protective layer and a preparation method thereof, and application of the polyurethane/polyurea composite protective layer in concrete shielding. The polyurethane/polyurea composite protective layer comprises a concrete base layer, a polyurethane elastic layer and a polyurea layer from bottom to top. The preparation method comprises the following steps: treating the surface of the concrete, and forming the polyurethane elastic layer by a multiple brushing or spraying method until reaching the designed thickness; and after the surface of the last brushing or spraying polyurethane layer becomes dry, spraying at least one polyurea layer to form the polyurethane/polyurea composite protective layer. The invention can be used for combined shielding of concrete surfaces in track traffic, parking lots, airports, roofs, road surfaces, playgrounds, sewage treatment plants, harbors, navigation locks, waterways, bridges, tubular piles and the like. The invention combines the elasticity, toughness and low price of the polyurethane with the shock resistance, wear resistance, corrosion resistance, aging resistance and other characteristics of the spraying polyurea to obtain the composite protective layer which has the advantages of excellent water resistance, excellent corrosion resistance, excellent shock resistance, high cost performance and high construction speed.