The lithium C-1-C-12 n-alkanoates (Li-carboxylates) were synthesized, and their thermal behavior was studied over the temperature range t/degrees C = (-30 to 600). Infrared and Raman spectroscopy indicated that the C-3-C-12 Li-carboxylates exist in two different configurations and that these configurations persisted after melting. In both configurations the equivalence of the C-O bonds were retained. Evidence for covalent character of the Li-O bond was found only for lithium methanoate. Solid-solid phase transitions were observed for all C-1-C-12 Li-carboxylates, with the exception of lithium butanoate, hexanoate, and octanoate. No liquid crystal phases were found for any of the C-1-C-12 Li-carboxylates. These observations were consistent with literature. A previously unreported solid-solid transition at temperature t/degrees C = (41.3 +/- 0.3) with enthalpy Delta H/kJ center dot kg(-1) = (2.8 +/- 0.1) was observed for lithium dodecanoate. The melting points of the C-1-C-2 Li-carboxylates were t/degrees C = (272 and 283) respectively. For the other Li-carboxylates, the melting points decreased monotonically from t/degrees C = (331) for lithium propanoate, to t/degrees C = (227) for lithium dodecanoate. The experimental values for melting point temperature and enthalpy of melting were consistent with literature. Thermal decomposition produced lithium carbonate (Li2CO3) as solid residue and took place at t/degrees C = (380 to 390) for C-1-C-2 Li-carboxylates and t/degrees C = (450 to 485) for C-3-C-12 Li-carboxylates.