Highly efficient proton conductors, polyoxometalate-poly(ethylene glycol) (POM-PEG) hybrid nanocomposites, have been synthesized by encapsulating a single PEG chain inside the 1D nanochannel defined by the frameworks of POMs. By employing two types of neutron scattering techniques complemented by thermal analysis, we prove that in a nanochannel a single PEG chain stays as a distorted helix. More importantly, we reveal that the PEG segments perform a localized longitudinal random walk and quantitatively show the strong correlation between the local motion of PEG and the macroscopic proton conduction of the material. On the basis of these spatial-temporal characteristics, a microscopic picture for the proton conduction process of POM-PEG hybrid materials is proposed.