PremiseChemical composition of floral volatiles can be an important complement to morphological characters in describing and identifying species. Four of the five species of western sessile‐flowered Trillium are challenging to distinguish morphologically due to wide intraspecific variation and overlapping characters among taxa. Characterizing their floral volatile compositions could aid future taxonomic, ecological, and evolutionary studies of Trillium and related taxa. We addressed two major questions: How do western sessile Trillium taxa vary in floral chemistry? Can floral scent be used to distinguish species?MethodsWe collected petals from 600 individuals at 42 wild populations of four sessile Trillium species across California, Oregon, and Washington. Volatile organic compounds from the petals were extracted using solid‐phase microextraction, and the volatiles were identified and quantified by gas chromatography–mass spectrometry. The utility of floral scent composition in distinguishing species was tested using nonmetric multidimensional scaling and random forest analysis.ResultsFloral volatiles of the white‐petaled T. albidum were dominated by oxygenated monoterpenes and showed considerable geographic variation that paralleled morphological variation. The maroon‐petaled T. angustipetalum and T. kurabayashii produced floral scents characterized by aliphatic esters, but each had a distinct chemical composition. Petal color of Trillium chloropetalum is highly variable, as were its scent compositions, which were blends of volatiles from both white‐petaled and maroon‐petaled congeneric taxa.ConclusionsDifferences in floral scent compositions are consistent with current taxonomy of the western sessile Trillium group. In cases where species delimitations are difficult based on morphology, floral scent composition provides taxonomic insight and suggests a potential hybrid origin for T. chloropetalum.