The complex of Sm2(o-NBA)6(PHEN)2 (o-NBA, o-Nitrobenzoate; PHEN, 1,10-phenanthroline) was prepar-ed and characterized by elemental analysis, IR and UV spectraoscopy. The thermal decomposition mechanism of Sm2(o-NBA)6(PHEN)2 was studied under a static air atmosphere by TG-DTG. The thermal decomposition kinetics of the complex for the first stage was studied under non-isothermal condition. The most probable mechanism functions of the thermal decomposition reaction for the first stage are: G(α)=[-ln(1-α)]1/2, f(α)=2(1-α)[-ln(1-α)]1/2. The activation energy E for the first stage is 259.50 kJ·mol-1, the pre-exponential factor A is 36.19×1018 min-1. The lifetime equation at weight-loss of 10% was deduced as lnτ=-36.70+27 572.12/T by isothermal thermogravimetric analysis.