Odor mixtures are perceived as different from (configural) or the same as (elemental) their components. Recent studies (L. M. Kay, C. A. Lowry, & H. A. Jacobs, 2003; C. Wiltrout, S. Dogra, & C. Linster, 2003) propose that component structural or perceptual similarities predict configural properties of binary mixtures. The authors evaluated this in rats using 4 binary mixtures with varying structural similarity (eucalyptol-benzaldehyde, eugenol-benzaldehyde, octanol-octanal, and [+/−]-limonene). The range of tested ratios for each mixture was determined by the components' vapor pressures. Three results are presented: (a) No mixture maintains purely elemental or configural properties for all concentration ratios, (b) structural similarity or dissimilarity does not predict configural or elemental perception, and (c) overshadowing is significant in responses to all odor sets. The authors offer more precise definitions of elemental and configural properties and overshadowing as they relate to odor mixture perception.