TG and DTA measurements of Cu-2(RCO2)(4) and Cu-2(RCO2)(4)py(2) (R = CH3(CH2)(n-2); n = 7, 8, 9, 10, 12) were done to their thermal behavior and establish the influence of pyridine in complexes on phase transition from solid state to compare liquid crystalline phase. Transitions from a crystalline to a liquid crystalline phase were observed for all Cu-2(RCO2)(4) compounds, but only for pyridine complexes of Cu(II) nonanoate, decanoate and dodecanoate. The transition temperatures for pyridine complexes are lower than that for corresponding Cu-2(RCO2)(4). Upon repeated heating just above the melting temperatures, Cu-2(RCO2)(4)py(2) complexes decompose to Cu-2(RCO2)4, which undergo the known crystalline to liquid crystalline phase transition at higher temperatures.