Tetra(3-pyridyl)porphyrazine is soluble in trifluoroethanol yielding intense blue solutions. The electronic spectra exhibit the characteristic Soret and Q bands around 330 and 610 nm, respectively; however, the absorption profile is strongly dependent on the concentration, reflecting the occurrence of an association process. The system has been elucidated by solving the equilibrium and the absorbance-concentration equations for all the wavelengths in the spectral range, according to a variational procedure. In this way the consistent spectra of the individual species have been generated. The study has also been extended to the luminescence properties of the porphyrazine molecule, and discussed in terms of the ground state association and the exciplex formation involving the monomeric species.