Poly(oxymethylene) dimethyl ethers (POMDMEs) open a new route for tailoring diesel fuels. POMDMEs belong to the group of oxygenates which reduce soot formation in the combustion when added to diesel fuels. They can be produced on a large scale based on gas-to-liquid technology. The present work first gives an overview of oxygenates as components of diesel fuels and process technology for their production. Then properties and chemistry of POMDMEs are discussed in detail. A particularly favorable route for their large scale production in which they are formed from methylal and trioxane is proposed and a feasible concept for this process is presented together with data on the reaction equilibrium that was taken in a batch reactor. (C) 2010 Elsevier Ltd. All rights reserved.