The influence of surface oxidation on the interaction between CH4 and amorphous AlYB14 (a-AlYB14) has been studied theoretically by using density functional theory and experimentally by ultra-high vacuum atomic force microscopy (UHV-AFM). CH4 mimics the-CH3 termination and aliphatic subunits of a polymer chain. Low-energy ion scattering measurements of magnetron sputtered thin films suggest that the bonding at the surfaces of pristine a-AlYB14 and 02 exposed a-AIYB14 (O-2//aAlYB(14)) is metal-boron and metal-oxygen dominated, respectively. Based on the 46 initio calculations the adsorption energies of CH4 on a-AlYB14 and O-2//a-AlYB14 decreases from -0.07 to -0.30 eV, respectively. This trend is consistent with experimental data obtained by colloidal probe UHV-AFM studies with a polyethylene sphere, where larger adhesion forces for the O-2 exposed surface as compared to the pristine a-AIYB(14) surface were measured. No charge transfer takes place between CH4 and the pristine as well as the O-2 exposed a-AlYB14. Oxygen chemisorption induces changes in surface bonding. States at the Fermi level are depleted upon oxidation, hence the surface bonding becomes more semiconducting causing a charge redistribution within the adsorbed CH4 molecule. Hence, these data serve as proof of concept for exploring the effect of O-2 exposure on the interaction between aliphatic polymers and a-AlYB14 using a correlative experimental and theoretical research approach. (C) 2016 Elsevier B.V. All rights reserved.