The role of secondary compounds (SC) in deterring herbivores and pathogens from vegetative parts of plants is well established, whereas their role in plant reproductive organs such as floral nectar is unclear. The present study aimed to reveal the response of free-flying honeybees to naturally occurring concentrations of four SC in floral nectar. We selected nicotine, anabasine, caffeine, and amygdalin, all of which are found in nectar of various plants. In repeated paired-choice experiments, we offered 20% sucrose solution as control along with test solutions of 20% sucrose with various concentrations of the above SC. Except for anabasine, naturally occurring concentrations of SC did not have a deterring effect. Furthermore, low concentrations of nicotine and caffeine elicited a significant feeding preference. SC can, therefore, be regarded as postingestive stimulants to pollinators, indicating that the psychoactive alkaloids in nectar may be a part of their mutualistic reward. Further studies are needed to test our hypothesis that psychoactive alkaloids in nectar impose dependence or addiction effects on pollinators.