Our knowledge of the composition of the waxes on the surfaces of Eucalyptus leaves is growing but that of plant primary metabolites has been completely overlooked. The diffusion of primary metabolites above the cuticle exposes them to a variety of herbivorous taxa and has the potential to influence their responses to that plant. Juvenile leaves of two families of Eucalyptus globulus Labill. ssp. globulus and two families of E. nitens (Deane & Maiden) Maiden had 11 out of 16 of the epicuticular waxes that were detected in common. However, two phenylethyl esters (waxes) were only detected on leaves of one family of E. globulus and two benzyl esters (waxes) were not detected or were uncommon in samples from E. nitens. Wax compounds were generally found in samples from both leaf surfaces but a few were only detected in samples from particular sides. Species and families of eucalypt did not differ significantly in the concentrations of free sugars, polyols, malic acid or γ-aminobutyric acid (GABA) (all plant primary metabolites) collected from the surfaces of leaves. However, concentrations of all these metabolites were usually higher in collections from the upper surfaces of leaves. High wax abundance, especially on the lower surfaces of E. globulus leaves, is suspected to have hindered dissolution of all the primary metabolites quantified. Several free amino acids exhibited significant species-level differences in concentrations, namely the aromatic, amide and sulfur-containing amino acids as well as proline; family-level differences in amino acid concentrations were not significant. Australian and overseas evidence showing that differences in waxes and primary metabolites can be influential in plant susceptibility to herbivorous taxa is considered with respect to the threats posed by the autumn gum moth and Mycosphaerella leaf spot fungi.