Long chain olefins are converted into aldehydes by hydroformylation using synthesis gas CO/H-2 and further converted in an acid-catalyzed conversion with glycerol in a one-pot procedure. Yields are up to 95 %. The obtained mixtures of 5- and 6-membered rings are potential fuel additives offering alternative use of glycerol from renewable resources. By optimization of reaction conditions such as catalyst precursor, ligand, pressure, temperature, solvent or catalyst/substrate ratio a highly selective hydroformylation towards linear acetals was achieved. For synthesis of larger amounts, glycerol was converted with alkenes on a 2-L-scale and with aldehydes on a 60-L-scale.