Densely packed polysaccharide brushes consisting of α-D-glucose residues were grafted from modified silicon substrates. Potato phosphorylase was herein used to grow linear polysaccharide chains from silicon tethered maltoheptaose oligosaccharides using glucose-1-phosphate as donor substrate. The combined use of potato phosphorylase and Deinococcusgeothermalis branching enzyme resulted in a hyperbranched brush coating as the latter one redistributes short oligosaccharides from the α(1-4)-linked position to the α (1-6)-linked position in the polysaccharide brush. The obtained grafting density of the brushes was estimated on 1.89 nm(-2) while the thickness was measured with ellipsometric techniques and determined to be between 12.2 and 20.2 nm.