The invention discloses a method for preparing rigid high-molecular medium with two kinds of pore forms by utilizing double emulsification, and said method includes the steps of selection of polymer monomer solution and pore-forming agent, formation of emulsion, polymerization reaction and washing, and it is characterized by that the monomer methyl glycidyl arylate, photoinitiator benzoin ethyl ether, emulsifier Span 80 and crosslinking agent ethylene dimethacrylate are formed into uniform mixed solution, the glycerine aqueous solution pore-forming agent is dispersed in mixed solution and formed into the emulsion liquor, said emulsion liquor can be formed into secondary emulsification in Tween 80 aqueou solution. The whole system can be undergone the process of UV photoinitiation suspension polymerization reaction under the condition of a certain rotating speed, after reaction the system is repeatedly washed by using water absolute ethyl alcohol so as to obtain the chromatographic separation medium with two pore form structures of super-large pore and diffusion pore.