In the leaf cuticular waxes of Myricaria germanica L. four different series of alkanediols were identified: (1) hentriacontanediol isomers with one functional group in the 12-position and a second group in positions ranging from 2 to 18, (2) C30-C34 alkanediols carrying one hydroxyl function on a primary and one on a secondary carbon atom. (3) homologous series of C25-C43 beta-diols predominantly with 8,10- and 10,12-functionalities, and (4) homologous series of C39-C43 gamma-diols with a predominance of 8,11- and 10,13-isomers. Primary/secondary diols and gamma-diols constituted only trace portions of the total wax mixture. The hentriacontanediols and the beta-diols amounted to 3.5 and 0.6 microg per cm2 of leaf surface area, corresponding to 9 and 2% of the wax mixture, respectively. Based on the different homolog and isomer patterns of respective diol fractions, two independent biosynthetic routes leading to the hentriacontanediols and the beta-diols are proposed.