Solid-state C-13 and H-1 NMR spectra of poly(ethylene oxide) (PEO)/LiCF3SO3 polymer electrolyte and quantum-chemical DFT calculations of C-13 and H-1 NMR chemical shifts on a diglyme/LiCF3SO3 model complex show a higher shielding of PEO (and diglyme) carbons and lower shielding of PEO (and diglyme) protons in the complex with LiCF3SO3, in comparison with neat PEO (diglyme). Both C-13 and H-1 chemical shifts are the same for PEO in amorphous and crystalline phases of PEO/LiCF3SO3 polymer electrolyte, showing essentially the same local structure in both phases. The effective distance between the LiCF3SO3 carbon and its nearest PEO protons in the PEO/LiCF3SO3 complex, determined from the Lee-Goldburg cross-polarization H-1-->C-13 dynamics, is in accord with the X-ray crystal structure. (C) 2004 Elsevier B.V. All rights reserved.