In social insect colonies, recognition of nestmates, kinship, caste and reproductive status is crucial both for individuals and for the colony. The recognition cues used are thought to be chemical, with the hydrocarbons found on the cuticle of insects often cited as being particularly important. However, in honeybees (Apis mellifera) the role of cuticular hydrocarbons in nestmate recognition is controversial. Here we use the proboscis extension response (PER) conditioning paradigm to determine how well honeybees learn long-chain linear alkanes and (Z)-alkenes present on the cuticle of worker bees, and also how well they can discriminate between them. We found large differences both in learning and discrimination abilities with the different cuticular hydrocarbons. Thus, the tested hydrocarbons could be classified into those which the bees learnt and discriminated well (mostly alkenes) and those which they did not (alkanes and some alkenes). These well-learnt alkenes may constitute important compounds used as cues in the social recognition processes.