The invention discloses an inorganic polymer exterior wall coating as well as a preparation method and application thereof. The coating is composed of water, a waterproof agent, a wetting dispersant,a defoaming agent, bactericide, 800-mesh light calcium carbonate, AMP-95, barium sulfate, rutile titanium dioxide, color paste, talcum powder, 4000-mesh calcined kaolin, styrene-acrylic emulsion, potassium silicate, dihydric alcohol, emulsified OP-10, water glass, a coalescing agent, polyvinyl alcohol, hydroxyethyl cellulose, ash calcium powder, mica powder, quartz powder, vanadium pentoxide, calcium fluoride, zinc phosphate, aluminum silicate, calcium pyrophosphate, sodium hydroxide and titanium oxide. The coating has excellent low-temperature film-forming property and thick-film cracking resistance, has Brinell viscosity of 20-80cps, is mildew-proof and heat-insulating, has silicate groups chemically reacted with a cement lime base material, permeates into a wall surface by 0.5-1mm to form a waterproof and acid-proof layer, and can avoid cracking, peeling and stripping.