The structures formed by the adsorption of poly(ethylene-co-acrylic acid) (PEA), poly(ethylene-co-vinyl alcohol) (EVOH), poly(ethylene-co-vinyl acetate) (EVA), and polyethylene (PE) on metal oxide powders were characterized by solid-state NMR spectroscopy and FTIR-PAS. The effect of the copolymer loading and the polar group density on the chain conformation and mobility were examined. In the case of the strongest polar group-substrate interactions, the chain conformation is determined by the sticker group density rather than the coverage until all the binding sites have been occupied. As the binding strength decreases, this trend diminishes, and there is a corresponding increase in the chain order as reflected by the C-13 chemical shifts of the ethylene segments. The chain conformation of the most weakly bound copolymer (EVA on alumina) shows no dependence on either the sticker group content or the coverage, similar to the homopolymer, PE. Some surface hydrolysis of EVA and of the residual ester groups of EVOH is also detected.