SUMMARYFoundresses and workers of Polistes paper wasps show slight morphological and physiological differences. However, after the emergence of the workers, the castes can be readily discriminated by their behaviour: the dominant foundress is the principal egg-layer, whereas workers perform different tasks linked to colony development. Previous studies have demonstrated in this genus that defence of the colony by the workers is more effectively carried out by a collective response elicited by venom volatiles used as alarm pheromones. In the present study, gas chromatography-mass spectrometry analyses of the venom volatiles of foundresses and workers of Polistes dominulus (Christ) show predominantly quantitative differences. Spiroacetals, mainly (E,E)-2,8-dimethyl-1,7-dioxaspiro[5.5]undecane, are significantly higher in the venom volatiles fraction of workers, whereas the amount of N-(3-methylbutyl)acetamide is almost double in foundresses. On the basis of the chemical results, behavioural assays were performed on fifteen field colonies to test the alarm response of the resident wasps to venom extracts from foundresses and workers. Our behavioural results suggest that worker venom has a stronger alarm effect on the colonies than that of the foundresses, which seems unable to elicit the complete alarm response ending with a final attack and sting. The venom volatiles of P. dominulus workers serve mainly to alarm the colony whilst those of foundresses may also be linked to additional functions related to conspecific interactions.