Thermoresponsive double hydrophilic block glycopolymer poly(N-isopropylacrylamide-co-6-O-vinyladipoyl-D-glucose)-b-poly(N-isopropylacrylamide) (P(NIPAm-co-OVAG)-b-PNIPAm) was prepared by a combination of enzymatic synthesis and reversible addition-fragment chain transfer (RAFT) polymerization protocols using P(NIPAm-co-OVAG) as a macro-RAFT agent. All the precisely synthesized glycopolymers were characterized by nuclear magnetic resonance spectroscopy and gel permeation chromatography. Detections using laser light scattering and transmission electron microscopy revealed that the block glycopolymer was able to self-assemble into micelles with various sizes and sphere morphologies in aqueous solutions. The glucose pendants in the glycopolymers had obvious interaction with lectin, concanavalin A (Con A), and their capacity of interaction with Con A was controlled by the number of glucose units in the glycopolymers. The block glycopolymer micelles have excellent biocompatibility with pig iliac endothelial cells using the MTT assay, however the glycopolymer–Con A micelles could be used to induce apoptosis in human hepatoma SMMC-7721 cells.