Perceptual interactions in a model of wine woody-fruity binary mixtures were previously reported in a psychophysical study performed through orthonasal stimulation only. However, recent studies suggested that the perception of food-like and nonfood-like odors may depend on the route of stimulation. The aim of the present study was two-fold: first to examine the neural correlates of perceptual interactions using electroencephalogram (EEG)-derived event-related potentials (ERPs) and second to test the influence of the stimulation route on quality perception. Therefore, we designed an experiment with 30 subjects to study perceptual interactions in woody-fruity mixtures and compared ortho- vs. retronasal stimulation sites on perceived odor quality and ERPs. The results revealed synergy or masking of the fruity component, depending on the woody component level. Synergy was supported by larger N1 amplitude of the ERP. Furthermore, mixtures including a medium level of the woody odor elicited a strong increase of P2 amplitude only retronasally. This study evidenced for the first time electrophysiological correlates of both perceptual synergy and masking on the early component of the ERPs and confirmed that retro- vs. orthonasal stimulation route induces different neural processes that are reflected in the late component of the ERP.