Three-dimensional MOFs, {[Cu3(tz)4Cl2] 2CH3OH}n (Htz = 1H-1,2,3,4-tetrazole), have been synthesized in methanol. It was characterized by chemical analysis, element analysis, IR spectroscopy, single-crystal X-ray diffraction and thermal analysis. Thermogravimetric analysis demonstrated that the MOFs after removing methanol molecules possessed good thermostability with decomposition temperature up to 533 K. The enthalpy change of liquid-phase formation reaction was determined by a RD496–2000 microcalorimeter at 298.15 K with the value of (−46.63 ± 0.26) kJ mol−1. The enthalpy change of solid-phase formation reaction was calculated as (−573.89 ± 0.89) kJ mol−1 on the basis of a designed thermochemical cycle. The thermodynamics of formation reaction of the MOFs was investigated by changing the temperature of liquid-phase reaction. Based on the experimental results, fundamental kinetic and thermodynamic parameters k, n, E, $$\Delta H_{ \ne }^{\theta }$$ , $$\Delta S_{ \ne }^{\theta }$$ and $$\Delta G_{ \ne }^{\theta }$$ were obtained. The specific heat capacity at 298.15 K was determined to be (1.87 ± 0.08) J K−1 g−1 by a RD496-2000 calorimeter. In addition, the constant volume combustion energy of title MOFs was determined by a RBC-II rotating-bomb calorimeter at 298.15 K. The standard molar enthalpy of combustion and standard molar enthalpy of formation were calculated to be (−4736.43 ± 4.03) kJ mol−1 and (293.42 ± 4.11) kJ mol−1, respectively.