Ultrafine biocompatible fibers decorated with carbohydrates were prepared by electrospinning. Both bulk- and surface-modification approaches have been investigated and compared in terms of practicability and grafting density along the fibrous mats. On one hand, bulk-functionalized fibers were prepared by electrospinning of native and galactose-modified PCL polymers. The size and morphology of the resulting fibers was strongly influenced by the galactose-PCL content as observed by electron microscopy. Successful surface modification was evidenced by water contact angle measurements, but a rather low carbohydrate density was attained, as indicated by a colorimetric quantification. On the other hand, efficient and versatile surface-glycosylation was achieved after modification of azido-functionalized electrospun fibers by CuAAC click-chemistry. Homogeneous ultrafine PCL fibers, decorated with azide functions, have been made completely hydrophilic upon coupling with propargyl-α-d-mannoside and propargyl-β-d-galactoside. Specific adhesion of lectins further attested good bioavailability of the surface carbohydrate residues, suggesting interesting perspectives of the latter approach in the development of bioactive materials for tissue engineering.