Oligomeric oxymethylene dimethyl ethers (OMEs) of the type CH3O-(CH2O)(n)-CH3 are promising diesel fuels with an enormous potential for the reduction of soot and NOx emissions. Oligomers with n = 3-5 are particularly advantageous, since their physicochemical and combustion properties are similar to conventional diesel. OMEs can be produced from methanol and formaldehyde but a series of byproducts, especially hemiformals, glycols, water and minor amounts of cyclic ethers, are also formed. These need to be separated from the product mixtures, which affects efficiency of this synthesis pathway. To isolate the desired OMEs, a one-step synthesis/extraction procedure is described. It implies highly selective extraction of OMEs from aqueous reaction solutions employing hydrocarbons as extraction agents. If fuel-type hydrocarbons are used, the resulting OME-hydrocarbon blends can be directly used in fuel applications. The corresponding oxymethylene diethyl ethers (OMDEEs) have also been investigated. Compared to OMEs, OMDEEs exhibit an increased solubility in nonpolar media but, as a result, solubility of educts and byproducts also increases. OME blends with hydrogenated vegetable oil and diesel have been prepared containing 10% of OMEs. It could be shown that such blends meet current diesel standards to a large extent.