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This book presents a wealth of results obtained by first-principles calculations, molecular dynamics simulations, and tight-binding modeling on two-dimensional covalent bonding and the resulting formation of 2D materials. It focuses on the bonding–structure relationships derived from the periodicity of the electron configuration and atomic size, paying particular attention to the overall stability of various elemental and composite networks. In addition to accurate first-principles calculations, the book uses a linear combination of atomic orbitals and the hybridization concept to gain deep insight into the rules governing the world of 2D chemistry. Introduction to Bonding, Structure, and Performance of Two-Dimensional Materials Elemental Group–IIA Monolayers Elemental Group–IIIA Monolayers Group IIA–IVA and IIIA–IVA Monolayers Elemental Group–IVA Monolayers Binary Heteroelemental Group IVA–IVA Monolayers Group IIIA–VA Monolayers Elemental Group–VA Monolayers Binary Heteroelemental Group VA–VA Monolayers Group IVA–VA Monolayers Elemental Group–VIA Monolayers Group IIIA–VIA Monolayers Group IVA–VIA Monolayers Group–IVB Transition-Metal Dioxide and Dichalcogenide Monolayers Group–VB Transition-Metal Dioxide and Dichalcogenide Monolayers Group–VIB Transition-Metal Dioxide and Dichalcogenide Monolayers Group–XB Transition-Metal Dioxide and XB Dichalcogenide Monolayers Summary and Outlook