The kinetics of the reaction CH3OCH3 + Fe+ has been studied between 250 and 600 K in the buffer gas He at pressures between 0.4 and 1.6 Torr. Total rate constants and branching ratios for the formation of Fe+O(CH3)(2) adducts and of Fe+OCH2 + CH4 products were determined. Quantum-chemical calculations provided the parameters required for an analysis in terms of statistical unimolecular rate theory. The analysis employed a recently developed simplified representation of the rates of complex-forming bimolecular reactions, separating association and chemical activation contributions. Satisfactory agreement between experimental results and kinetic modeling was obtained that allows for an extrapolation of the data over wide ranges of conditions. Possible reaction pathways with or without spin-inversion are discussed in relation to the kinetic modeling results.