We have determined the static structure factor for a poly(ethylene oxide) (PEO) melt from neutron scattering and atomistic molecular dynamics simulations. The experimental total structure factors for protonated and deuterated samples were found to be in good agreement with simulation. The calculated partial structure functions facilitate the interpretation of features in the total radial distribution function in the 5-15 Angstrom range and comparison is made with previous work on poly(ethylene). Using hydrogen-deuterium isotope substitution methods, the intermolecular H-H pair distribution function was determined. Unlike a previous comparison for polyethylene, only qualitative agreement between experiment and simulation for the intermolecular H-H pair distribution function was obtained.