Polyoxymethylene dimethyl ethers (PODEs) are an excellent blend for diesel due to their high cetane number, high oxygen content, and low viscosity. Combustion and emission characteristics are investigated based on experimental tests on a turbocharged, in-line 6-cylinder, common rail diesel engine. Results show that combustion starts earlier with PODE blending at low and partial loads. With pilot and main injection, the peak combustion pressures and peak heat release rates of diesel/biodiesel/PODE blend fuels increase due to large amounts of reactive radicals formed in the pilot heat release stage. With an increase in load, a slight decrease in both peak combustion pressure and peak heat release rate is observed. At low loads, the CA10s, CA50s, and CA90s of diesel/biodiesel/PODE blend fuels advance, and both rapid combustion and late combustion phases shorten. At medium and high loads, CA10s advance, CAS0s remain unchanged, and CA90s clearly advance. Rapid combustion phases increase very little, whereas the late combustion phases clearly shorten. Combustion durations shorten in each engine operation. It can be concluded that the addition of PODE is helpful for more concentrated heat release. As a result, combustion temperatures increase. The NOx emissions of blend fuels arise with PODE at 1400 and 2000 rpm, whereas soot emissions obviously decrease. In particular, diesel/biodiesel/PODE blends reduce soot emissions significantly at medium and high loads and reduce the number concentrations of ultrafine particles at low and partial loads.