Alien species must adapt to new biogeographical regions to acclimatise and survive. We consider a species to have become invasive if it establishes negative interactions after acclimatisation. Xylella fastidiosa Wells, Raju et al., 1986 (XF) represents Italy’s and Europe’s most recent biological invasion. In Apulia (southern Italy), the XF-encountered Philaenus spumarius L. 1758 (Spittlebugs, Hemiptera: Auchenorrhyncha) can acquire and transmit the bacterium to Olea europaea L., 1753. The management of XF invasion involves various transmission control means, including inundative biological control using Zelus renardii (ZR) Kolenati, 1856 (Hemiptera: Reduviidae). ZR is an alien stenophagous predator of Xylella vectors, recently entered from the Nearctic and acclimated in Europe. Zelus spp. can secrete semiochemicals during interactions with conspecifics and prey, including volatile organic compounds (VOCs) that elicit conspecific defence behavioural responses. Our study describes ZR Brindley’s glands, present in males and females of ZR, which can produce semiochemicals, eliciting conspecific behavioural responses. We scrutinised ZR secretion alone or interacting with P. spumarius. The ZR volatilome includes 2-methyl-propanoic acid, 2-methyl-butanoic acid, and 3-methyl-1-butanol, which are consistent for Z. renardii alone. Olfactometric tests show that these three VOCs, individually tested, generate an avoidance (alarm) response in Z. renardii. 3-Methyl-1-butanol elicited the highest significant repellence, followed by 2-methyl-butanoic and 2-methyl-propanoic acids. The concentrations of the VOCs of ZR decrease during the interaction with P. spumarius. We discuss the potential effects of VOC secretions on the interaction of Z. renardii with P. spumarius.