Both the radical anion and radical cation of 2,7,12,17-tetraphenylporphycene and of its palladium(II) complex have been produced by photochemical methods. Their electronic absorption spectrum and decay kinetics have been characterised by global analysis of the time-absorbance-wavelength matrix. The results provide deeper insight on the role of these radical ion species in the photodynamic activity of tetraphenylporphycenes.