This chapter contains figures illustrating electronic structure of lead (Pb) (Group IVA metal), and bismuth (Bi) (Group VA metal). This chapter illustrates i) parameterized density of states (DOS’s) for Pb, ii) XPS spectra of Pb, iii) distance between the image plane and the last atomic layer, for the (111), (100) and (110) faces of Pb, iv) self-consistent pseudopotential calculation of the electronic structure of the Pb(001) surface. Experimental and calculated energy band along the ΓT direction of Bi is illustrated. The calculated surface density of states is also presented. Dispersion of surface state energy of Bi is shown.