Over the last two decades, poly(ethylene oxide) (PEO). one of the model solid polymer electrolytes, has been investigated by various techniques. Neutron scattering using spin polarised neutrons with spin polarisation analysis provides a unique opportunity to study both the structure and dynamics in the same experiment. This is feasible due to the experimental separation of the coherent and incoherent scattering, and it gives increased confidence in the models proposed. Using this technique. we studied PEO complexed with lithium triflate, LiSO3CF3, at different concentrations, below and above T-g. PEO below its glass transition has a strong tendency to crystallise, and even above T-g, displays considerable short-range older, In turn. this affects the analysis of the dynamics of the matrix (hence conductivity). The results obtained are compared with those obtained by others.