A polygeneration process with the ability to provide work, heat, and useful chemicals according to the specific demand is a promising alternative to traditional energy conversion systems. By implementing such a process in an internal combustion engine, products like synthesis gas or unsaturated hydrocarbons and very high exergetic efficiencies can be obtained through partial oxidation of natural gas, in addition to the already high flexibility with respect to the required type of energy. To enable compression ignition with natural gas as input, additives such as dimethyl ether are needed to increase the reactivity at low temperatures. In this study, the reaction of fuel-rich natural gas/dimethyl ether (DME) mixtures is investigated to support the further development of reaction mechanisms for these little studied reaction conditions. Temperature-resolved species concentration profiles are obtained by mass spectrometry in a plug-flow reactor at equivalence ratios phi = 2, 10, and 20, at temperatures between 473 and 973 K and at a pressure of 6 bar. Ignition delay times and product-gas analyses are obtained from shock-tube experiments, for phi = 2 and 10, at 710 - 1639 K and 30 bar. The experimental results are compared to kinetic simulations using two literature reaction mechanisms. Good agreement is found for most species. Reaction pathways are analyzed to investigate the interaction of alkanes and DME. It is found that DME forms radicals at comparatively low temperatures and initiates the conversion of the alkanes. Additionally, according to the reaction pathways, the interaction of the alkanes and DME promotes the formation of useful products such as synthesis gas, unsaturated hydrocarbons and oxygenated species. (C) 2020 The Combustion Institute. Published by Elsevier Inc. All rights reserved.