Using a conditioning paradigm, the olfactory sensitivity of three squirrel monkeys and three pigtail macaques for homologous series of aliphatic 2-ketones (2-butanone to 2-nonanone), symmetrical ketones (3-pentanone to 6-undecanone), and C7-ketones (2-heptanone to 4-heptanone) was assessed. In the majority of cases, the animals of both species significantly discriminated concentrations below 1 ppm from the odorless solvent, and with 2-nonanone and 5-nonanone the monkeys even demonstrated thresholds below 1 ppb. The results showed both primate species have a well-developed olfactory sensitivity for aliphatic ketones, and pigtail macaques generally perform better than squirrel monkeys in detecting members of this class of odorants. Further, in both species tested, we found a significant negative correlation between perceptibility in terms of olfactory detection thresholds and carbon-chain length of both the 2-ketones and the symmetrical ketones, but not between detection thresholds and position of the functional group with the C7-ketones. These findings lend further support to the growing body of evidence suggesting that between-species comparisons of the number of functional olfactory receptor genes or of neuroanatomical features are poor predictors of olfactory performance.