In this study, we used differential scanning calorimetry (DSC) to study pyrolysis kinetics of zinc acetylacetonate (Zn(acac)2) in chamber ambient simulating real CVD condition, with heating rate from 10 to 20 °C/min. For Zn(acac)2 heated in pure N2, inert environment, DSC showed three endothermic peaks locating at 91–106 °C, 121–128 °C, and 135–142 °C, with peak area being 88 KJ/mol, 14 KJ/mol, and 18 KJ/mol, respectively. The DSC residuals analyzed by IR indicated all peaks might be originated from physical phenomena, since no compositional change observed. Further study by temperature programmed polarized optical microscope (POM) showed these peaks might be related to dehydration, phase transition, and melting of Zn(acac)2 and its hydrates. DSC in oxygen-containing ambient with O2 concentration from to 13 to 40 % showed three endothermic peaks and two additional exothermic broad peaks at higher temperature, 209–236 °C, and 330–400 °C. These exothermic peaks are assigned to oxidative decomposition of Zn(acac)2 and releasing of ligands. When oxygen concentration increased, peak area grew. Positions of these peaks depend on heating rate. Increasing the heating rate caused every peak to shift toward higher temperatures, with the first two endothermic peaks merged into one broad one.