Nanometer-scale thick liquid films of poly(methylhydro-dimethyl)siloxane copolymer (PMDMS) deposited on hydrophilic and hydrophobic solid organic films have been studied using synchrotron X-ray specular reflectivity (XRR). The physico-chemical properties of liquid PMDMS at the interfacial level are controlled by the nature of the solid surface. Detailed analysis of the XRR-data revealed the formation of a low-density region in the liquid PMDMS film in the vicinity of the hydrophobic surface, whereas a densely packed molecular layer is formed at the liquid PMDMS-hydrophilic substrate interface. Non-covalent polymer chains are 'frozen' at the solid-liquid interfaces in the confined liquid films and interactions with the substrate surfaces (i.e. hydrogen bonding) are responsible for distinctly different density profiles.