A novel adsorption material of alpha-, beta- and gamma-cyclodextrin (CD)/ Poly(acrylonitrile) (PAN) composite nanofibers was prepared via electrospinning. The PAN composite nanofibers were applied to Cu (II) ion adsorption, which is suitable for Cu (II) ion adsorption due to their high adsorption affinity for metal ions. The amounts of the metal ions adsorbed onto alpha-, beta- and gamma-CD/PAN composite nanofibers mats were influenced by alpha-, beta- and gamma-CD concentration and the contact time. The physicochemical properties and adsorption performance of alpha-, beta- and gamma-CD/PAN composite nanofibers were characterized.