To address current challenges related to climate change, novel concepts, such as engine-based polygeneration under fuel-rich conditions, have recently been developed. In this context, understanding and validation of the associated chemical kinetics are a key factor for prediction and optimizations. In this work, the combined effect of ozone and DME as additives on the partial oxidation of natural gas mixtures is investigated in a plug-flow reactor at a pressure of 4 bar and at temperatures ranging from 373 to 973 K. Double-imaging photoelectron photoion coincidence (i²PEPICO) spectroscopy measurements are presented to study the conversion of the reactants and the formation of main products, and to identify important intermediates responsible for the low temperature chemistry phenomena and ignition characteristics of the natural gas/dimethyl ether/ozone mixture. Among the activation effect of ozone, the temperature-variant ozone dissociation at elevated pressures up to 20 bar is studied for the first time, revealing the start of ozone decomposition at 423 K in the investigated pressure range. In addition, the ozone decomposition is shown to be slightly pressure-dependent in the pressure range between 1 and 20 bar with lower ozone conversions at higher pressures. The experimental results are compared with model predictions using literature reaction mechanisms for validation and further analysis. The ozone decomposition initiates fuel conversion and the formation of oxygenates and hydroperoxides at very low temperatures, i.e., 423 K, resulting in an overall three-stage oxidation process at ∼450 K (1. stage), ∼550 K (2. stage), and ∼750 K (3. stage). Also, the overall fuel conversion is enhanced in the intermediate temperature range (between 550 K and 750 K) by up to 40%-points. The hydroperoxides, among other species, are clearly identified by mass-selected threshold photoelectron spectra from the literature. Excellent agreement between experiments and simulations is found, while deviations are observed for some oxygenates at very low temperatures showing the need for further model improvements.