The invention provides a preparation method of macroporous long alkyl side chain acrylic acid ester-styrene-ethylene dimethacrylate crosslinking copolymerization microballoon. The invention relates to macroporous long alkyl side chain acrylic acid ester-styrene-ethylene dimethacrylate crosslinking copolymerization microballoon and a preparation method thereof. In the preparation method, oil-soluble benzoyl peroxide is an initiator, long alkyl side chain acrylic acid ester, styrene and ethylene dimethacrylate are monomers, a suspension polymerization method is employed, an aqueous solution containing a dispersant and salt is water phase, and the monomers containing the initiator and a pore forming agent are mixed as stable oil phase. Under protection of nitrogen, the oil phase is stirred and subjected to a polymerization reaction at a certain temperature, and a resultant is subjected to filtering, washing, Soxhlet extraction, and vacuum drying treatments to obtain the macroporous crosslinking copolymerization microballoon. The above synthetic method has the advantages of safety, easy separation of products, low production cost, easy control of temperature, stable product quality the like, and is suitable for large scale industrial production. Since having porous and hydrophobic characteristics, the hydrophobic macroporous microballoon disclosed in the invention has a substantial advantage in removing enriched hydrophobic organic pollutants in water, which is a prospective environment friendly adsorption material and can be effectively used for processing relative organic waste water. The hydrophobic macroporous microballoon also has potential application value in fields of catalyst and drug carrier, bioseparation and the like.