The valence shell is the outermost shell of an atom, which contains the electrons most likely to account for the nature of any reactions involving the atom and of the bonding interactions it has with other atoms. Electrons in the valence shell are referred to as valence electrons. The chemist Gilbert Newton Lewis was responsible for much of the early development of the theory of the participation of valence shell electrons in chemical bonding. Linus Pauling later generalized and extended the theory while applying insights from quantum mechanics.

In a noble gas, an atom tends to have 8 electrons in its outer shell (except helium, which is only able to fill its shell with 2 electrons). This serves as the model for the octet rule which is mostly applicable to main group elements of the second and third periods. In terms of atomic orbitals, the electrons in the valence shell are distributed 2 in the single s orbital and 2 each in the three p orbitals.

For organometallic compounds containing transition metals, the valence shell consists of electrons in these s and p orbitals, as well as up to 10 additional electrons, distributed as 2 into each of 5 d orbitals, to make a total of 18 electrons in a complete valence shell for such a compound. This is referred to as the eighteen electron rule.