Nanofibrous sugar sticks with linear PANCGAMA and cyclic PANCAG glucose pendants were fabricated by electrospinning from acrylonitrile-based glycopolymers. Field emission scanning electron microscope was used to characterize the morphologies of the nanofibers. Utilizing the specific carbohydrate-protein interaction, these two kinds of nanofiber mats were applied to separate the protein mixtures. Con A and BSA were used as model proteins. The Con A/BSA mixture solution was isolated successfully by selective adsorption of Con A to the cyclic glucose pendants on the PANCAG nanofibrous sugar sticks. However, PANCGAMA nanofibers showed almost no selectivity for these two proteins due to the poor specificity between linear glucose pendants and Con A.