Associational herbivore resistance is potentiated by neighbouring heterogenic plant species that impact a focal plant’s attraction to herbivores or the damage that they cause. One mechanism to confer associational resistance is believed to be exposure to neighbour-emitted volatiles, the receivers of which range from intra- and interspecific neighbour plants to higher-trophic-level insects. In previous studies the passive adsorption of neighbour-emitted semivolatiles has been reported, but little is known regarding the mechanisms and ecological consequences on the receiver plant and its associated biota. To utilize volatile-based associational resistance for agricultural applications, it is imperative to know its effectiveness under varying diurnal temperatures and whether herbivore natural enemies, providing biological control, are impacted. Mimicking varying diurnal temperatures in a laboratory set-up, we assessed how the tritrophic model system Brassica oleracea var. italica (broccoli)–Plutella xylostella (crucifer specialist herbivore)–Cotesia vestalis (endoparasitoid of P. xylostella) is influenced by exposure to the natural semivolatile emitter plant Rhododendron tomentosum Harmaja.