The invention relates to a styrene-bifunctionality monomer copolymer hollow porous microsphere and a preparation method of the styrene-bifunctionality monomer copolymer hollow porous microsphere, wherein styrene, a bifunctionality dimethyl acrylate organic monomer and a photoinitiator are dissolved in a solvent to obtain an electrospray solution, the styrene-bifunctionality dimethyl acrylate monomer copolymer hollow porous microsphere is prepared through electrostatic spraying under the visible light, the inner part of the prepared microsphere is hollow, the surface of the prepared microsphereis porous and has a crosslinking structure, the crosslinking structure is formed by mutually crosslinking of molecular chains of a styrene-bifunctionality dimethyl acrylate monomer copolymer, and themelting temperature of the styrene-bifunctionality monomer copolymer hollow porous microsphere is more than 500 DEG C. The preparation process of the method is simple and convenient, the melting temperature of the prepared hollow microsphere is high, the microsphere keeps the three-dimensional structure in the melt processing, the role of the microsphere is fully played, the range of applicationof the hollow microsphere structure in the practical use is expanded, and the microsphere has a quite excellent promotional value.