Polymer electrolytes based on poly(ethylene glycol) dimethyl ether (PEGdME) and the ionic liquid (IL) 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim]PF6) have been prepared and characterized by different techniques. Coordination of the IL by the polymer occurs mainly in the amorphous phase. This finding was correlated with previous theoretical investigations of a similar model for polymer electrolytes based on poly(ethylene oxide), PEO, and IL. It has been obtained ionic conductivity σ ∼10−3 Scm−1 for the polymer electrolyte with 35wt% of IL at 100°C. The same order of magnitude for σ was obtained by molecular dynamics simulation of PEO/IL. This work demonstrates consistency between experimental and theoretical results for polymer electrolytes containing ionic liquids.