The invention discloses crosslinked polysiloxane/acrylic ester compound emulsion, and a preparation method and application thereof. The preparation method comprises the following steps: performing shear emulsification and high-pressure homogenization on an organic siloxane monomer, water and a composite emulsifier to prepare a siloxane monomer emulsion; adding a crosslinking agent to prepare a crosslinked polysiloxane emulsion; and compounding the crosslinked polysiloxane emulsion and a polyacrylic ester emulsion, which is prepared by a continuous emulsion polymerization method, by a simple process to obtain the stable and high-compatibility crosslinked polysiloxane/acrylic ester compound emulsion. The crosslinked polysiloxane/acrylic ester compound emulsion has the characteristics of excellent hydrophobicity, low-temperature resistance, high-temperature resistance, water tolerance, alkali resistance, stain resistance and the like of olysiloxane emulsion as well as the characteristics of film-forming property, weather resistance, ozone resistance, uvioresistant capability and the like of acrylic emulsion and can be applied to building paint of inner walls, outer walls, floors, bathrooms and the like.