Thermal behaviors of two mixed-ligand complexes, [Ni(PMPP-SAL)(Py)3] and [Cu(PMPP-SAL)Py]·MeOH, (PMPP-SAL=1-phenyl-3-methyl-4-(salicylidene hydrazide)-propenylidene-pyrazolone-5, Py=pyridine), were studied by TG-DTG-DTA in dynamic air atmosphere. The complexes show the loss of pyridine molecule is followed by the decomposition of the PMPP-SAL anion and give respective metal oxides as residues. Meanwhile, the Ozawa-Flynn-Wall model-free analyses and multivariate non-linear regressions were applied to perform single and overall steps optimization. Kinetic parameters were given and the most probable mechanism functions were suggested in this study.