AbstractA survey of linalool enantiomers in kiwifruit (Actinidia) flowers was conducted to determine their potential as sources of these valuable floral fragrances, and revealed a wide range of enantiomeric ratios. While flowers of A. polygama and A. chrysantha contained almost exclusively one enantiomer, most species contained significant amounts of both (R) and (S) isomers. In some species enantiomeric ratios of floral linalool differed between genotypes, full siblings, and in one case clones, and ratios changed from year to year as well as diurnally. Enantioselective biosynthesis of the linalool‐derived furanoid and pyranoid linalool oxides was examined in flowers of an A. chrysantha and an A. polygama genotype. The flowers of both species produced almost exclusively (S)‐linalool. A. chrysantha flowers incubated with rac‐d5‐linalool preferentially processed the (S)‐isomer through to the linalool oxides. However, the A. polygama flowers were less discriminatory in their use of rac‐d5‐linalool and processed significant quantities of d5‐(R)‐linalool as well. Chirality, 2010. © 2009 Wiley‐Liss, Inc.