During the formation of metal–semiconductor contacts two principally different types of electronic states are effective in determining the surface position of the Fermi level within the semiconductor band gap. These are, first, adatom‐related surface states of donor character and, second, the continuum of adsorbate‐induced interface states which result from the tailing of the metal wave functions into the virtual gap states of the semiconductor band structure. The first type of state is observed at submonolayer coverages either after depositions at low temperatures or even at room temperature when a cation exchange occurs. Each metal adatom contributes one of those surface donors and their energy levels are linearly correlated with the first ionization energies of the metal atoms. The second type of state exists at interfaces under metallic islands and continuous metallic films. The charge transferred across the interface by these tails of the metal wave functions is explained by the difference in electronegativities of metal and semiconductor in analogy to the concept of the partial ionic character of covalent bonds.