We employ atomistic computer modeling to investigate the structure and morphology of poly(ethylene oxide) (PEO) chains confined in 1-nm slit pores defined by montmorillonite silicate layers. Molecular dynamics computer simulations reveal the Li+ cations to be located in the immediate vicinity of the silicate surfaces and PEO to adopt highly amorphous conformations in a liquidlike bilayer across the slit pores. Despite the orienting influence of the parallel stacked silicate walls, PEO shows no indication of crystallinity or periodic ordering; in fact, for all temperatures simulated, it is less ordered than the most disordered bulk PEO system. These amorphous PEO film configurations are attributed to the combination of severe spatial confinement and the strong coordination of ether oxygens with the alkali cations present in the interlayer gallery. These conclusions challenge the picture traditionally proposed for intercalated PEO, but they agree with a plethora of experimental observations. Indicatively, the simulation predictions are confirmed by wide-angle neutron scattering and differential scanning calorimetry experiments on PEO/montmorillonite intercalates. (C) 2003 Wiley Periodicals, Inc.