Raman and infrared spectroscopy were used to investigate hydrogen-bonding interactions and cation coordination effects in solutions of lithium triflate (LiCF3SO3) dissolved in two primary amines, hexylamine (HEXA) and N,N-dimethylethylenediamine (DMEDA), and in a secondary amine, dipropylamine (DPA). Strong intermolecular hydrogen-bonding interactions and weaker intramolecular hydrogen-bonding interactions that occur only in DMEDA were spectroscopically distinguished in a comparison of pure HEXA, pure DMEDA, and the dilute solutions of these amines in CCl4. The spectroscopic shifts in intensity and frequency in the NH stretching region of DPA and DPA diluted in CCl4 were similar to those of HEXA. Dilute electrolyte solutions in carbon tetrachloride were prepared to analyze specifically the cation coordination effect. In these solutions, limited intermolecular hydrogen-bonding interactions are present, and the observed spectral shifts correspond primarily to the cation-induced shifts. The symmetric SO3 stretching region of the triflate anion was investigated to probe further the coordination of the cation. The local structures of the triflate ions and the amine groups in the electrolyte solutions dissolved in CCl4 are similar to the local structures in the corresponding amine-salt crystals previously reported by us.