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L-edges absorption spectra of FePc (I) and FePc(η-O) (II) on Ag(110) have been modelled using the DFT/ROCIS method. Despite disregarding the presence of the substrate, the agreement between experiment and theory is remarkable. Moreover, theoretical results confirm the fraction of II (70%) present on the surface, thus allowing a thorough assignment of each experimental spectral feature. Ground state (GS) theoretical outcomes pertaining to I and II provide an intimate understanding of the electron transfer pathway ruling the I-based catalytic oxygen reduction reaction. DFT/ROCIS outcomes indicate that the lower excitation energy (EE) side of the L intensity distributions mainly includes states having the GS number of unpaired electrons (two in I and six in II), whereas states with higher/lower spin multiplicity contribute to the L higher EE side. The occurrence of states involving metal to ligand charge transfer transitions implying low lying empty π∗ ligand-based orbitals on the L higher EE sides have been confirmed., The Italian Ministry of the University and Research (PRIN-2010BNZ3F2, project DESCARTES), the University of Padova (CPDA134272/13, project S3MArTA), and the Computational Chemistry Community (C3P) of the University of Padova are kindly acknowledged. This work has been partially financed by the Spanish projects MINECO MAT2014-53921-R and DGA IMANA E34.