Raman spectroscopy was used to study ionic association and polymer conformation in methoxyl end capped PPO (M-PPO) doped with NaCF3SO3, for temperatures ranging from 230-340 K. M-PPO of molecular weights 400 to 2000, pure and doped with sodium triflate of concentration O:M = 15:1, were studied in order to investigate the importance of the end groups for ionic solvation. It is found that in M-PPO, in contrast to OH-terminated PPO, the number of dissociated ions is independent of molecular weight. Moreover, the ion-association in the M-PPO systems was found to be comparable to that reported for OH-PPO of molecular weight 4000 indicating that the latter is an excellent low molecular analogue to higher molecular weight systems. Furthermore, the absence of a distinct polarised metal-oxygen breathing mode in the M-PPO salt complexes indicates a polymer-ion interaction different from the symmetric configurations of chains wrapped around cations as suggested for PEO based polymer electrolytes. The solvation model of cations forming cross-links via coordinations to ether oxygens of adjacent chains is favoured.