Thermal properties of cycloalkanecarboxylates [Rh-2(O2CR)(4)] (R = C3H5, C4H7, C5H9 and C6H11) were studied and the results compared with those obtained for [Rh-2(O2CR)(4)] (R = CH3, C2H5 and C3H7). Thermogravimetry and differential scanning calorimetry were used as the techniques and the heats of reaction for the samples in open and closed crucibles were obtained, in different atmospheres.