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This study investigated the event-related brain potentials associated with the olfactory-visual cross-modal Stroop effect and its modulation by olfactory-induced and self-reported affective states. Eighteen healthy participants were presented with an olfactory stimulus and the image of a plant, and they had to categorize the olfactory attribute of the image as “aromatic” or “pungent” by pressing the relevant button as quickly as possible. The type of olfactory-visual stimuli (congruent or incongruent) and the valence of the olfactory-induced emotional states (positive or negative) were manipulated following a 2 × 2 factorial design. Interference effects were observed at the behavioral and the electrophysiological levels: response times recorded in the incongruent condition were higher than those observed in the congruent condition; an incongruent minus congruent negative difference component was discovered between 350 and 550 ms after stimulus onset in the negative—but not in the positive—olfactory-induced emotional state condition. This ND350-550 component was interpreted as reflecting the amount of selective attention involved in the olfactory-visual cross-modal Stroop effect. These results are also consistent with a facilitatory effect of positive emotional state on selective attention which could reduce brain potentials associated with the cross-modal interference effect.