Construction of starburst C-60(> DPAF-C-9)(4) pentads was coupled with the use of highly fluorescent diphenylaminofluorene-C-9 (DPAF-C-9) addends as donor components in conjunction with the fullerene acceptor during single-photon excitation processes. High quantum yields (Phi(CS)) of charge-separation processes in the range 0.83-0.90 for C-60(> DPAF-C-9)(n) (n = 1, 2, or 4) were obtained in the formation of C-60(center dot-)(> DPAF(center dot+)-C-9)(> DPAF-C-9)(n-1) transient states. The lifetime of the radical ion-pairs (tau(RIP)) was found to be 900 ns for starburst C-60(> DPAF-C-9)(4) (3) samples, which is 6-fold longer than that of the linear analogue C-60(> DPAF-C-9) (1), with a ca. 2 times increase of the charge-separation rate (k(CS)) compared to that of 1. These data implied the important role of sterically hindered DPAF-C-9 pendants arranged in a starburst-like environment that encapsulates the central C-60 core on extending the tau(RIP). We interpreted the phenomena by the occurrence of intramolecular migration or exchange of electron or positive charge among multiple DPAF-C-9 pendants of C-60(center dot-)(> DPAF(center dot+)-C-9)(> DPAF-C-9)(n-1), which gives an increased rate in charge generation and delayed charge recombination.