Plant-ant interactions are generally considered as mutualisms, with both parties gaining benefits from the association. It has recently emerged that some of these mutualistic associations have, however, evolved towards other forms of relationships and, in particular, that plants may manipulate their partner ants to make reciprocation more beneficial, thereby stabilizing the mutualism. Focusing on plants bearing extrafloral nectaries, we review recent studies and address three key questions: (i) how can plants attract potential partners and maintain their services; (ii) are there compounds in extrafloral nectar that could mediate partner manipulation; and (iii) are ants susceptible to such compounds? After reviewing the current knowledge on plant-ant associations, we propose a possible scenario where plant-derived chemicals, such as secondary metabolites, known to have an impact on animal brain, could have evolved in plants to attract and manipulate ant behaviour. This new viewpoint would place plant-animal interaction in a different ecological context, opening new ecological and neurobiological perspectives of drug seeking and use.