The phenomena of aggregation and coalescence of fullerenes in the UV-laser ablation time-of-flight mass spectrometric investigation of C-60-modified poly(N-vinylcarbazole) both in the positive and in the negative ion channels have been observed. The results indicate that in C-60 chemically modified PVK (C-60-PVK) copolymer the nascent fullerene fragments ruptured from main chain can easily coalesce into large fullerenes through collisions, whereas in the C-60-doped PVK the aggregation and coalescence of C-60 were relative weak due to nonbounding action and incomplete charge transfer behavior between C-60 and PVK. Furthermore, the photoinduced electron transfer behavior between C-60 and carbazole units in the C-60 chemically modified poly(N-vinylcarbazole) in benzonitrile by laser flash photolysis at 355 nm has also been investigated. Efficiency of the anion radical of C-60 in copolymer at 1080 nm is higher than that of the C-60-doped poly (N-vinylcarbazole) polymers. The formation of a C-60 radical anion may be ascribed to photoinduced electron transfer between C-60 pendanted on the main chain backbone and the inter-, and intrachain carbazole units in the copolymer.