On the basis of the assignment of methylene proton signals in (1)H NMR and determination of the chemical shift difference (Deltadelta), the relative configuration of 1,3,n-methyl-branched deoxypropionates can be determined directly. Comparison of the chemical shifts in the corresponding syn- and anti-configured compound pairs shows remarkable differences, while the absolute values depend on the presence and nature of adjacent functional groups. The determination of the Deltadelta values provides a reliable assessment of the relative configuration in 1,3,n-methyl-branched polypropionate chains and is even valid for macrocycles.