Dimethyl Ether (DME) has proved to be a promising fuel for diesel engines. It virtually eliminates particulate emissions and reduces the formation of nitrogenous oxides, without negatively affecting engine efficiency. Obtaining a deeper understanding of the mechanisms behind these properties is thus highly desirable. Various authors have suggested that the low NO emissions associated with DME are an effect of the mixing conditions, which are thought to differ from those of diesel sprays. To examine this, laser-Rayleigh imaging was employed for quantitative measurement of the local equivalence ratios in DME sprays. The quantitative images were analyzed using a statistical approach, in which probability distributions of ϕ-values for burning and for non-reacting sprays were compared. It was concluded that the diffusion flame is established in the stoichiometeric or slightly lean regions of the spray. Measurements were performed in an isochoric combustion vessel chemically preheated by igniting a lean mixture of CO and oxygen-enriched air. A multizone combustion model was used to analyze the DME combustion and the effects of preheating on the vessel atmosphere. The benefits and drawbacks of this set-up are discussed.