Summary: The teeth of limbed vertebrates used for capturing and processing food are composed of mineralized dentine covered by hypermineralized enamel, the hardest material organisms produce. Here, we combine scanning probe microscopy, depth sensing, and spectromicroscopy (SR-FTIR) to characterize the surface ultrastructural topography, nanotribology, and chemical compositions of mammal species with different dietary habits, including omnivorous humans. Our synergistic approach shows that enamel with greater surface hardness or thickness exhibited a more salient gradient feature from the tooth surface to the dentino-enamel junction (DEJ) one that corresponds to the in situ phosphate-to-amide ratio. This gradient feature of enamel covering softer dentine is the determining factor of the amazingly robust physical property of this unique biomaterial. It provides the ability to dissipate stress under loading and prevent mechanical failure. Evolutionary change in the biochemical composition and biomechanical properties of mammalian dentition is related to variations in the oral processing of different food materials.