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Olfaction is the oldest sense in the animal kingdom. It is used during a multitude of behaviours, such as the encounter of food, the detection of predators, the recognition of habitat‐related cues or the communication with conspecifics. While the use of olfaction and chemical communication has been studied widely in some animals, it is barely known in others. Anurans (frogs and toads), for example, are well known to use acoustic and visual senses, but their chemical sense is still largely understudied. Studies concerning the chemical sense in anurans have been mostly based on the use of semiochemicals in juvenile stages, while the information on adult anurans remains limited. In this study, we analysed the behavioural response of the Neotropical poison frog Ranitomeya sirensis (Sira poison frog, Dendrobatidae) when presented with the odours of prey, novel/prey‐luring fruit, habitat, conspecific faeces and heterospecifics. For this, we offered each of the odours by placing them into one of two testing tubes fixed in an arena, with the other tube left empty as a control. We then measured the time the frogs spent in the vicinity of the odour versus the control tube and calculated a response index. While the frogs did not show a significant avoidance or attraction towards most of the tested odours, they showed a strong response towards the heterospecific odour, which was significantly avoided. This is the first evidence of a poison dart frog responding towards the odours of adult heterospecific frogs. We consider potential reasons for this strong negative reaction, such as the interspecific competition avoidance hypothesis, and discuss our results in the context of other animal species being deterred or attracted by heterospecific chemical cues. [ABSTRACT FROM AUTHOR]