Ultraviolet photoelectron spectroscopy (UPS) has been applied to investigate the valence electronic structures of the double-decker type phthalocyanine compound, bis(phthalocyaninato)tin(IV) (SnPc 2 ). The binding energies of spectral features were precisely determined and compared to those of tin(II) and lanthanide compounds. Two peaks were observed at 5.1 1 and 6.0 4 eV in the lower binding energy region, which corresponded to the molecular orbitals generated by the anti-bonding and bonding interactions between the orbitals of the two phthalocyanine rings, respectively. It is worthy to note that the ionization threshold of SnPc 2 is remarkably small as compared to other phthalocyanine compounds, implying ease of oxidation. Actually, oxidized forms of SnPc 2 were easily obtained by both chemical and electrochemical reactions, and their electronic structures were discussed in comparison with that of SnPc 2 and with the recent results of the density functional theory calculations.