A new, simple, and effective synthetic method for the preparation of glucose-terminated polyisobultylenes starting from the corresponding hydroxyl-terminated polymers reported. Detailed NMR and matrix-assisted laser desorption/ionization mass spectrometric (MALDI-TOF MS) investigations showed the exclusive presence of bis(glucopyranosyl) polyisobutylene. Dynamic light scattering (DLS) investigations of this polymer in solution in both tetrahydrofuran and water showed that microphase separation takes place by the formation of micelles and/or vesicles.