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Polyoxymethylene dimethyl ethers (PODEn) are promising alternative fuel candidates for diesel engines because they present advantages in soot reduction. This study uses a PODEn mixture (contains PODE3-6) from mass production to provide oxygen component in blend fuels. The spray combustion of PODEn-diesel bend fuels in a constant volume vessel was studied using high speed imaging, PLII-LEM and OH* chemiluminescence. Fuels of several blend ratios are compared with pure diesel. Flame luminance data show a near linear decrease tendency with the blend ratio increasing. The OH* images reveal that the ignition positions of all the cases have small differences, which indicates that using a low PODEn blend ratio of no more than 30% does not need significant adjustment in engine combustion control strategies. It is found that 30% PODEn blended with diesel (P30) can effectively reduce the total soot by approximately 68% in comparison with pure diesel.