The magnetic circular dichroism (MCD) spectrum and assignment of the characteristic 'fingerprint band' of the pi -cation radical of phthalocyanine complexes are studied using a semiempirical MO method. Two types of excited configurations from occupied e(g) orbitals to the a(1u) singly occupied molecular orbital (SOMO) were present between Q band and B-band manifolds. The magnetic dipole moments of the two configurations were similar in magnitude but the signs were opposite. Because of the vicinity in energy, the two excited configurations couple to give an excited state, 2E(g), having an extremely reduced A term. The 'fingerprint band' is assigned to this state.