Adsorption of poly(ethylene glycol), hydrophobically end-capped with octadecenylsuccinic anhydride (OSA-PEG-OSA), on an ultrathin film of cellulose has been studied by quartz crystal microbalance with dissipation monitoring (QCM-D) and atomic force microscopy (AFM). Normally, PEG does not adsorb on cellulosic surfaces, but the use of the telechelic hydrophobic modification was found to promote adsorption. The influence of the conformation of the polymer in solution prior to adsorption and the subsequent properties of the adsorbed layer were investigated. The adsorption experiments were done at concentrations below and above the critical association concentration. The adsorption of OSA-PEG-OSA on cellulose was observed to occur in four distinct stages. Because of the amphiphilic nature of cellulose, further adsorption experiments were performed on hydrophobic (polystyrene) and hydrophilic (silica) model substrates to illuminate the contribution of hydrophobic and hydrophilic factors in the adsorption phenomenon. As expected, the kinetics and the mechanism of adsorption were strongly dependent on the chemical composition of the substrate.