Blending aromatic mixtures components naturally fuse to form a unique odor - a configuration- qualitatively different from each component's odor. Repeated exposure to the components either in the mixture or separately, favors respectively, configural and elemental processings. The neural bases of such processes are still unknown. We examined the brain correlates of the experienced-induced configural processing of a well-known model of binary blending odor mixture, the aromatic pineapple blending (AB, ethyl maltol + ethyl isobutyrate). Before fMRI recording, half of the participants were repeatedly exposed to the mixture (AB, group Gmix), with the other half exposed to its separate components (A and B; Gcomp). During the fMRI recording, all participants were stimulated with the mixture (AB) and the components (A and B). Finally, participants rated the number of odors perceived for each stimulus. Gmix perceived the AB mixture as less complex than did Gcomp. While Gcomp perceived the mixture as more complex than its components, Gmix did not. These results show the presence of experience-induced configural or elemental processing of the AB mixture in each group. Contrasting the brain activity of Gcomp and Gmix, when stimulated with AB, revealed higher activation in the left orbital part of the inferior frontal gyrus. This result sheds light on this area's function, commonly found activated in olfactory studies, and closely connected with the lateral orbitofrontal cortex. We discuss the role of this area as a mediator of configural percepts between temporal and orbitofrontal areas involved in configural memory processes.