A method for the separation of C4 olefin mixtures using anion-pillared hybrid porous materials as physical adsorbents is provided. The anion-pillared hybrid porous material was constructed by metal ions (M), organic ligand (L), and inorganic anion (A), forming a three-dimensional structure (A-L-M). C4 olefin mixtures contact with hybrid porous materials in certain ways, then each single C4 olefin monomer can be obtained. The pore size of anion-pillared hybrid porous materials and the spatial configurations of the anions within the pores can be fine-tuned and pre-designed. C4 olefins with different size and shape can be efficiently separated by the anion-pillared hybrid porous materials through shape recognition and size-sieving mechanism.