Identification of the electronic states of manganese phthalocyanine close to the Fermi level

► The electronic states of Mn and Cu phthalocyanine close to the chemical potential have been determined by a combined experimental and theoretical approach. ► The highest occupied molecular orbital of MnPc has been identified to be of strong metal 3d character in contrast to CuPc. ► The 0.5 eV lower ionization potential of MnPc can be rationalized in consideration of the difference of the HOMO wave functions.