The main goal of this work was to develop a supramolecular chemistry strategy to decorate interfaces with polyethylene glycol (PEG) grafts. A series of novel bifunctionalized dextrans, bearing 40-60 PEG pending chains and 12-24 hydrophobic adamantyl groups, have been prepared by copper(I)-catalyzed azide-alkyne cycloaddition. Their binding properties toward native βCD and βCD polymers were characterized both in solution and at interface using isothermal titration microcalorimetry and surface plasmon resonance. The polymers were found to form stable layers onto neutral and positively charged βCD-polymer films pre-adsorbed on gold surfaces, due to multivalent interpolymer host-guest interactions. The thickness and stability of the layers could be tuned by varying the ratio between the degrees of substitution by PEG and adamantyl groups.