The NOx emission characteristics of dimethyl ether (DME) in laminar co-axial jet and counterflow non-premixed flames were investigated using experimental and numerical approaches, respectively. The flame structure and NOx emissions of DME were compared to those of C2H6, which has equivalent methyl structures but lacks an oxygen atom. Experimental results showed that, in the co-axial jet case, the combustion of DME had the characteristics of a partial premixed flame. Additionally, it had a shorter flame and lower NOx emissions compared to the C2H6 flame. It is thus concluded that the major cause of low NOx emissions from DME co-axial jet flames may be the short flame length because of the lower stoichiometric air/fuel ratio. The activation of reburning NO chemistry because of the characteristics of the partially premixed flame may also play a role. The computational results of the DME counterflow non-premixed flame revealed that the EINO decreased by approximately 50% relative to that of the C2H6 flame. Although the overall NOx reaction path of the DME flame is similar to that of the C2H6 flame, it is concluded that the DME non-premixed flame has a distinct NO reduction mechanism. This is associated with reburning NO chemistry in the fuel-rich region because of fast pyrolysis and oxidation reactions in comparison to that of the C2H6 flame.