Temperature-responsive polymer surfaces based on modified high molar mass polyglycidol were obtained via the “grafting onto” technique. The solid support (glass or silica) was modified to introduce reactive anhydride groups. The covalent bonding of the temperature-responsive poly(glycidol-co-ethyl glycidyl carbamate) to the base support was obtained by the chemical reaction between reactive functional groups on the support and on the polymer. The surface properties, such as the composition, morphology, thickness and wettability, and their changes with the temperature were investigated using Fourier Transform Infrared Analysis, Atomic Force Microscopy, ellipsometry and contact angle measurements, respectively. The attachment of the hydrophobically modified polyglycidol derivatives produced a polymer layer with a thickness of 20–60nm and a changeable philicity due to the temperature alterations. This unique behavior was applied to the investigation of the interaction of polymer nanolayers with skin cells (fibroblasts and keratinocytes). The skin cells adhesion to the poly(glycidol-co-ethyl glycidyl carbamate) surface was possible at temperatures above the phase separation temperature, when the polymer layer was hydrophobic.