The molar heat capacities of one-three-dimensional metal–organic frameworks (MOFs) Cr3F(H2O)2O(BDC)3 (Cr-MIL-101) were measured by temperature-modulated differential scanning calorimetry over the temperature range from 253 to 413 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 atomic absorption spectrometer, elemental analysis, powder XRD and FTIR spectrum. Moreover, the thermal decomposition characteristics of Cr-MIL-101 were investigated by thermogravimetry–mass spectrometer (TG–MS). Three stages of mass loss were observed in the TG curve. TG–MS curve indicated that the oxidative degradation products of Cr-MIL-101 are mainly H2O and CO2.