In this work, thermal oxidation reaction of dimethoxymethane (DMM) at low temperature was investigated with a custom-designed mini closed pressure vessel WA (MCPVT) employed. The initial auto-oxidation, thermal decomposition and deep radical oxidation processes were revealed by analyzing the behavior of oxidation temperature (T) and pressure (P) in the process of MCPVT monitoring. Peroxides generated from DMM autooxidation were measured by iodimetry and thin-layer chromatography (TLC). The dominant peroxide was separated from oxidation products via column chromatography, with structure characterized by mass spectrometry (MS), H-1 and C-13 nuclear magnetic resonance (NMR). The thermal decomposition characteristics were determined by differential scanning calorimeter (DSC). Results show that the oxidation was mainly initiated by hydrogen abstraction on the methylenedioxy (O-CH2-O) of DMM when temperature was above about 310 K. The primary product of hydroperoxide, hydroperoxy(methoxymethoxy)methane was found in DMM oxidation for the first time, with a high level. Its exothermic onset temperature (T-0) and decomposition heat (Q(DSC)) are 372.87 K and 2431.37 J.g(-1), respectively. The thermal decomposition could lead to thermal runaway of oxidation, and further transform into an explosion. In most cases, the release of radical pool after peroxides decomposition would induce a rapidly radical oxidation of DMM through an endothermic reaction at about 410 K.