Photoinduced intramolecular processes in a dyad of azulene and C-60 (Az-C-60) were compared with those of a dyad of naphthalene and C-60 (Naph-C-60) on the basis of laser flash photolysis experiments. Upon photoexcitation of C-60 in the presence of azulene, intermolecular electron transfer proceeded from azulene to the triplet state of C-60 (C-60(T-1)), although the rate constant was small (10(7) M-1 s(-1)), because of the small free-energy change for electron transfer via C-60(T-1). In Az-C-60, it was revealed that the S-2 state of the Az moiety (Az(S-2)-C-60(S-0)) donates the excited energy to the C-60 moiety, effectively generating Az(S-0)-C-60(S-1). In polar solvents, a charge-separated state (Az(.+)-C-60(.-)) was generated from Az(S-0)-C-60(S-1), from which the S-1 state of the Az moiety (Az(S-1)-C-60(S-0)) was also generated by competitive energy transfer. The lifetimes of the charge-separated states were on the order of nanoseconds. Successive energy-transfer processes {Az(S-2)-C-60(S-0)--> Az(S-0)-C-60(S-n), Az(S-0)-C-60(S-1) --> Az(S-1)-C-60(S-0), where n greater than or equal to 2} demonstrate that the multiple energy transfer is achieved in a simple dyad molecule. On the other hand, Naph-C-60 dyad did not show charge separation upon excitation of the C-60 moiety, but deactivated via intersystem crossing, generating almost quantitatively the C-60(T-1) moiety. These findings indicate the favorable donor ability of azulene compared to that of naphthalene, even though both azulene and naphthalene have the same 10-pi-electron system.