The reaction kinetics of dimethoxymethane (DMM) towards H atom abstraction by hydroperoxy and methyl peroxy radicals were investigated using the G4 composite method. All the studied reactions were found to be endothermic and non-spontaneous in nature. Canonical Variational Transition State Theory in combination with Small Curvature Tunneling corrections were adopted to calculate the rate coefficients in the temperature range of 400–1500 K. The Arrhenius expressions for the reaction of DMM with CH3OO[rad] and HO[rad]2 radicals were obtained as ktotal = 1.50 × 10−12 exp (−8159/T) and ktotal = 4.40 × 10−12 exp (−7251/T) cm3 molecule−1 s−1 respectively. © 2020 Elsevier B.V.