The invention relates to a nanometer silica sol modified exterior wall emulsion paint. The emulsion paint comprises, by mass, 10-30% of water, 15-30% of an emulsion, 5-10% of a nanometer silica sol, 5-15% of heavy calcium, 1-3% of talc, 0.5-1.5% of propylene glycol, 5-25% of titanium dioxide, 0.05-2% of a wetting agent, 0.5-1% of an antifoaming agent, 0.1-0.5% of a dispersant, 1-2% of a thickening agent, and 0.5-2% of a film forming assistant. The preparation method comprises the following steps: dispersion grinding: adding water, powders and early assistants to a dispenser, grinding, and filtering; and post-treating: adding the emulsion, the nanometer silica sol, later water and later assistants to a dispersed slurry, and adjusting the PH value and the viscosity to prepare the emulsion paint. According to the invention, the exterior wall emulsion paint, which is prepared by completing simple technologies of dispersing, sand milling, filtering and the like, has the advantages of no pollution, low VOC (volatile organic compound) discharge, environmental protection, strong adhesion, and good storage stability, washing resistance, contamination resistance and weather resistance.