Males of the green–veined butterfly Pieris napi synthesize and transfer the volatile methyl salicylate (MeS) to females at mating, a substance that is emitted by non–virgin females when courted by males, curtailing courtship and decreasing the likelihood of female re–mating. The volatile is released when females display the ‘mate–refusal’ posture with spread wings and elevated abdomen, when courted by conspecific males. Here, we assess how the amount of MeS released by courted females changes over time since mating, and whether it is influenced by the frequency with which females display the mate–refusal posture. We also assess whether males tailor the anti–aphrodisiac content of ejaculates with respect to the expected degree of sperm competition, by comparing how males allocate MeS proportionately to first and second ejaculates in relation to ejaculate mass. The results show that females housed for 5 days in individual cages where they were able to fly and oviposit normally, released similar amounts of MeS. However, females housed together for the same period of time, causing them to frequently display the mate–refusal posture, released significantly lower levels of MeS than the individually housed females. This indicates that female display of the mate–refusal posture depletes their anti–aphrodisiac stores, and suggests that females are unable to voluntarily control their release of the anti–aphrodisiac. A comparison of relative proportion of MeS transferred by males in their first and second ejaculates showed that proportionately more MeS was allocated to the first ejaculate, in accordance with the idea that these are tailored to delay female re–mating.