The molar heat capacities of one–three-dimensional metal–organic frameworks Al4(OH)2(OCH3)4(H2N-BDC)3 (CAU-1) were measured by temperature-modulated differential scanning calorimetry (TMDSC) over the temperature range from 213 to 393 K for the first time. No phase transition or thermal anomaly was observed in the experimental temperature range. The fundamental thermodynamic parameters such as entropy and enthalpy relative to 298.15 K were calculated based on the experimentally determined molar heat capacities. The compound was characterized by elemental analysis, powder XRD, FT-IR spectrum. Moreover, the thermal stabilities and decomposition mechanisms of hydrated phase and dehydrated phase of CAU-1 were investigated by thermogravimetric spectrometer in the temperature range 298–1023 K.