Abstract：The coordination compound of Cu(Ⅱ) with N,N,N',N"-tetra[(1'-n- butyl-2'-benzimidazol) methyl]-trans-1,2-diaminocyclohexane (NBUOCTB), [Cu(NBUOCTB)](ClO~4)~2.2DMF, was prepared. The compound crystallizes in space group Pban with a=1.2553(2), b=2.0022(8), c=2.5687(5)nm, Z=4. The thermal decomposition process of the compound has also been studied using TG-DTG techniques under non-isothermal condition. The experimental data were analyzed through the combination of integral and differential methods. The first thermal decomposition stage belongs to "Coring and Growth (n=1)" mechanism and conforms to Avrami-Erofeev equation. The second stage is "Two-order Chemical Reaction".