The ruthenium benzimidazolylidene-based N-heterocyclic carbene (NHC) complex 4 catalyzes the direct dehydrogenative condensation of primary alcohols into esters and primary alcohols in the presence of amines to the corresponding amides in high yields. This efficient new catalytic system shows a high selectivity towards the conversion of diols to polyesters and of a mixture of diols and diamines to polyamides. The only side product formed in this reaction is molecular hydrogen. Remarkable is the conversion of hydroxytelechelic polytetrahydrofuran ((M) over bar (n) = 1000 g mol(-1))a polydispers starting materialinto a hydrolytically degradable polyether with ester linkages ((M) over bar (n) = 32 600 g mol(-1)) and, in the presence of aliphatic diamines, into a polyether with amide linkages in the back bone ((M) over bar (n) = 16 000 g mol(-1)).