The oxo-diperoxo-molibdenum(VI)-potassium oxalate, K2[MoO(O2)2(C2O4)] was synthesized using an adapted version of the method suggested by Dengel. The thermal behavior of the synthesized complex was investigated by simultaneous thermal analysis TG/DTG/DTA, in air or nitrogen atmosphere, to identify and characterize the mass-loss decomposition processes. In addition, for the characterization of the observed decomposition steps, the FT-IR spectra for the initial complex, evolved gaseous compounds and isolated complex at 230 and 430/383 °C in air/nitrogen atmosphere, were recorded. On the 35–500 °C temperature range, the K2[MoO(O2)2(C2O4)] complex presented three main decomposition steps, accompanied by mass-loss. The first degradation step is due to the elimination of one oxygen molecule, by the breaking of the peroxo groups, with the formation of an intermediary, like [MoO3L]. The other two degradation steps can be attributed to the decomposition of the organic ligand, with the final formation of a stable metallic oxide.