The nonlinear absorption and refraction of octasubstituted metallophthalocyanines (R 8 PcM: M = 2H, Cu) in solution is measured in the picosecond regime by the Z-scan technique at a wavelength of 1.064 μm. The results at different pulsewidths show that the nonlinear absorption process is dominated by two-photon absorption in the metal-free compound, and by excited state absorption in the Cu-substituted molecule.