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To explore the effect mechanism of polyoxymethylene dimethyl ethers (PODE)-diesel blends on nitric oxide (NO) and soot emission characteristics, the in-cylinder pressure and the emissions of blends with PODE volume fraction at 10%, 20%, and 30% (labeled P10, P20, and P30) are tested, also the in-cylinder working process of a diesel engine at 2600 r/min under 100% load is simulated by using a computational fluid dynamics software. The results show that both the in-cylinder temperature and the concentration of oxygen atoms have an important effect on the emissions of PODE-diesel blend fuels. PODE helps to increase the average combustion temperature and oxygen atom distribution range in the cylinder, thus reducing the range of lean combustion zone with uneven mixture. With the addition of PODE, the ignition delay period of PODE-diesel blend fuel is shortened, speeding up the combustion process. When the blending ratio of PODE is increased, an ascent of NO production and NO concentration distribution is observed, while soot emissions are significantly reduced, and the ultimate soot generation of P30 fuel under the calibrated working condition is decreased by nearly 80% compared with diesel. [ABSTRACT FROM AUTHOR]