Femtosecond transient absorption studies were conducted for self-assemblies between oppositely charged metal-substituted 18-crown-6 tetrasubstituted phthalocyanines (McrPc) and metal-substituted meso-(4-sulfophenyl)-porphine (MTPPS) or meso-(4-carboxylphenyl)-porphine (MTPPC). Excitation could be carried out at 400 nm (Ti-Sapphire second harmonic), which populates the porphyrin-localized S-2 state or directly into the CT band (690), and was achieved by changing the pump pulse wavelength with an optical parametric amplifier. Each complex showed the transient features and kinetics that were independent of the excitation wavelength. After 400 nm excitation, all complexes displayed rapid conversion to the low-lying charge-transfer state. Studies of the CuP/CuPc complex showed no significant decay of the transients on the subnanosecond time scale. However, investigations of the complexes containing different transition metals showed that deactivation of the complex excited state occurs through metal-centered (d,d) states. For the mixed metal/free-base complexes, the excited-state relaxation occurred through the metallotetrapyrrole component regardless of whether it was porphyrin or phthalocyanine. In these compounds, the charge transfer state deactivated to form the metal-centered (d,d) state within 2 ps, with lifetimes that varied somewhat with the metal center. This latter state repopulated the ground state with a lifetime of ca. 13 ps (NiP/NiPc), 200 ps (NiP/CuPc), 8 ps (CuP/NiPc), and 7 ps (FbP/CoPc). These metal-to-ground state rates were similar to those measured for the monomeric metallotetrapyrroles.