Recent studies have demonstrated that cultivar mixtures can reduce aphid plant acceptance and population development. It is still unknown as to which underlying mechanisms may contribute to this phenomenon. We investigated the effects of volatile interactions between undamaged barley cultivars on aphid feeding behavior and performance in the laboratory. Spring barley (Hordeum vulgare L.) cultivar Salome was exposed to volatiles from Fairytale (SeF), Anakin (SeA), or clean air (Se0). We used an electrical penetration graph to test the effect of exposure to neighbor volatiles on the feeding behavior and performance of bird cherry-oat aphids (Rhopalosiphum padi L.). We also assessed aphid relative growth rate, intrinsic rate of increase, and development time on exposed and unexposed Salome plants. Aphids spent significantly longer time on epidermis and mesophyll plant tissues on SeF than Se0, and no difference was observed between SeA and Se0. Significant decreases in the duration of phloem ingestion and phloem sustained ingestion were recorded in SeF showing that volatile-induced effects cause difficulty for aphids to feed. However, no differences in these variables were detected between SeA and Se0. We also observed reduced aphid relative growth rate and intrinsic rate of increase on SeF compared to Se0 and SeA. Our study demonstrated that, in a specific combination, exposure of one barley cultivar to volatiles from another one can change aphid feeding behavior and performance, probably due to changes in host plant properties/quality. Our results provide an insightful explanation of mechanisms responsible for the reduced aphid population development previously observed in the field.