Materials whose valence states consist of atomic s and p orbitals are commonly referred to as sp materials. The book introduces to the theory of electronic structure calculations for sp materials and studies the sp materials boron, lithium and aluminum. The biggest part of the book is dedicated to the investigation of novel phases of elemental boron, where boron sheets, boron nanotubes, and layered boron bulk materials are explored. Then a new route to achieve control over the atomic structure of nanotubes during their synthesis is proposed. Finally, the author presents the first realization of the generalized pseudoatom concept introduced by M. A. Ball, which is called enatom. A method to construct the enatom is established, whose potential is to obtain a real-space understanding of solids, their vibrational properties, and electron-phonon interactions.