Systems of linear poly(ethylenimine), LPEI, with dissolved LiCF3SO3 and NaCF3SO3 have been studied using Raman and infrared spectroscopy. As the salt concentration is increased in the LPEI–LiCF3SO3 system, in turn “free” ions, contact ion pairs and the triple cation [Li2CF3SO3]+ each become the dominant species present, whereas contact ion pairs appear to be the dominant ionic species over the same composition range in the LPEI–NaCF3SO3 system. One of the major effects of adding salts to LPEI is the breaking of hydrogen bonds in the host polymer. As the salt concentration is increased in both systems, a somewhat abrupt onset of band broadening and widespread loss of band structure is observed.