An atom's outermost electrons are called valance electrons. These valence electrons are the ones that are transferred (in the case of ionic bonds) or shared (in the case of covalent bonds).
Only the valence electrons of atoms can interact; the inner electrons do not form bonds.
A sodium atom, for example, has a total of 11 electrons -- two complete the first shell, eight complete the next shell, and a single electron occupies the outer shell. This single atom is a valence electron.