Crystal of rare earth perchlorate complex compound with proline was synthesized. By using TG, DTA and chemical analytic method, and comparing with relative literatures, its structure was characterized as [Gd2(Pro)6(H2O)4](ClO4)6, and it has a purification of 99.0% . A thermochemical cycle was designed at 298.15K, measurements of solution calorimetry of the reactants [2GdCl3· 6H2O+ 6Pro+ 6NaClO4· H2O] and the products {[Gd2(Pro)6(H2O)4](ClO4)6+ 6NaCl} were carried out in an isoperibel reaction calorimeter, respectively. The calorimetric solvent used was 2mol· L- 1 HCl. The chemical reaction and standard enthalpy of formation were calculated as: =- 46.829kJ· mol- 1, ([Gd2(Pro)6(H2O)4](ClO4)6,s,298.15K)=- 6532.745kJ· mol- 1.