The invention discloses a W/O/W multiphase emulsion and a method for preparing hierarchical pore SiO2 microspheres using the W/O/W multiphase emulsion as a formwork. The multiphase emulsion uses micromolecular compounds as a stabilizing agent, uses a silylating reagent as an oil phase, and uses a hydrochloric acid aqueous solution of which the pH is 2-5 as an aqueous phase; the W/O/W multiphase emulsion is prepared by a one-step method, and the prepared emulsion is uniform in the distribution of liquid drops. According to the preparation method disclosed by the invention, the W/O/W multiphase emulsion is used as a formwork, the hierarchical pore SiO2 microspheres are prepared by a reaction under ammonia atmosphere, the operation is simple and easy, the cost is low, and the method is environmental-friendly; the prepared SiO2 microspheres have rich multistage pore canal structures, and the pore canal structures are regular, and good in permeability; besides, the SiO2 microspheres have large specific surface areas and high heat stability, the hydrophilic-hydrophobic property is adjustable, the carried functional groups are adjustable, and the SiO2 microspheres can be applied in the varied fields of adsorption, separation, catalysis, medicines and the like.