<p>Both polyoxymethylene dimethyl ethers (OME_<i>n</i>) and biodiesel are considered as promising alternatives or additives to traditional fuels. The addition of OMEs to biodiesel can realize complementary advantages. The physical properties of OME_<i>n</i>, biodiesel, or OME_<i>n</i>/biodiesel blends are decisive for the performance of internal combustion engines. In this work, density and viscosity of mixtures of OME_<i>n</i> with three typical components of biodiesel (methyl decanoate, methyl dodecanoate, and methyl tetradecanoate) were measured from 303.15 K to 333.15 K at atmospheric pressure. The vibrating-tube method and capillary-tube method were used for the present density and viscosity measurement, respectively. The combined relative uncertainty is 0.1% for density and 1.5% for viscosity (<i>k</i> = 2). The experimental results were fitted by Jouyban-Acree model and McAllister model. Moreover, the excess properties of each mixture including excess molar volume and viscosity deviations were discussed.</p>