The Apocynaceae–Asclepiadoideae are well known for their specialized floral morphologies and pollination systems and many species have distinct floral aromas. However, our knowledge on the chemistry of floral volatiles in this plant family is relatively limited although it has been suspected that floral scent plays a key function for pollinator attraction. This is the third paper in a series of papers reporting on the floral odours of Asclepiadoideae. Floral odours of eleven species from seven genera (Cibirhiza, Fockea, Gymnema, Hoya, Marsdenia, Stephanotis and Telosma) of early diverging taxa of Apocynaceae–Asclepiadoideae, and two species of Secamone (Apocynaceae–Secamonoideae) were collected using headspace sampling and then analyzed via GC–MS. We detected 151 compounds, of which 103 were identified. The vast majority of chemicals identified are common components in flower odour bouquets of angiosperms. However, striking was the high relative amount of acetoin (97.6%) in the flower scent of Cibirhiza albersiana. This compound has rarely been reported as a flower scent component and is more commonly found in fermentation odours. Bray–Curtis similarities and Nonmetric-Multidiminsional Scaling (NMDS) analyses showed that each of the species has a distinct odour pattern. This is mostly due to only twelve compounds which singly or in different combinations dominated the scent of the species: the benzenoids benzyl acetate, benzaldehyde, methyl benzoate, and 2-phenylethyl alcohol; the monoterpenoids (E)-ocimene, (Z)-ocimene, linalool, and eucalyptol; and the aliphatic compounds acetoin, and (E,Z)-2,6-nonadienal. The floral scent compositions are discussed in relation to tribal affiliations and their potential role for pollinator attraction, and are compared with the scent data available from other Asclepiadoideae species.