The invention belongs to the technical filed of water paint, which particularly relates to nanometer hollow silica sphere/polyurethane compound water paint and the process for preparation thereof. The water compound paint is chemically compounded by hollow SiO2 sphere, whose dimension is 50-250 nanometers, isocyanate terminated polyurethane prepolymer, catalyst and other auxiliary agents. Indoor temperature storage stability of the compound water paint is excellent, nanometer hollow SiO2 sphere and water polyurethane have excellent compatibility, hardness and compatibility of the water compound coating layer are greatly improved, and fire-resisting property and ultraviolet resistant performance are excellent. The process for preparation of the invention has the advantages of convenient and simple technique, high film coating quality, low production cost and extensive application prospect and the like, which has no pollution to environment, the water paint is a new generation environmental-friendly high-performance chemical product, which can be applied in the fields such as automobile coating, wood coating, construction, office furniture, leather, textile finishing, pigment printing and mechanical equipment.