A unique feature of the glandular trichomes of Solanaceae species is their production of sugar esters. These metabolites have been shown to possess insecticidal, antifungal, and antibacterial properties. Sugar esters produced by tobacco (N. tabacum) provide resistance to insects such as budworms, and are important precursors of the organoleptic components. Acyl moieties of the sugar esters in Nicotiana spp., petunia, and tomatoes vary with respect to carbon length and isomer structure (2 to 12 carbon chain length; ante-iso-, iso-, and straight-chain). The objective of this work was to catalog information about the diversity of acyl group composition among species, cultivars, and accessions in Nicotiana and Petunia. Sugar esters from individual plant species were sampled according to an established protocol, and butyl esters of the acyl groups were analysed by GC-MS. The amounts of each group were calculated in moles and expressed as mole%. We studied acyl groups in 21 accessions of Nicotiana obtusifolia, six accessions of N. hesperis, three of N. alata, two of N. occidentalis, four modern cultivars of commercial tobacco, and five petunia hybrids. We observed a total of 21 different acyl groups that were represented differently among cultivars, species, and accessions. In Nicotiana species, acetate and the iso- and ante-iso branched acids prevailed. Straight-chain acyl groups (2 to 8 carbons) were present in the petunia hybrids, while octanoic acid was found in N. alata and N. sanderae. Two unexpected acyl groups for the genus Nicotiana, 8-meNonanoate and decanoate, were found in sugar esters of N. occidentalis subsp. hesperis. Sugar esters and their acyl groups could serve as a model in which to explore the basis of phenotypic diversity and adaptation to natural and agricultural environments. Natural or modified sucrose esters may prove useful in foliar applications to protect crops against various pests, or other uses.