The photoaggregation dynamics of chemically bonded C 60 PVK and C 60 /PVK mixture was studied by laser ablation TOF mass spectrometry. The enhancement of coalescence of fullerene cages in chemically bonded C 60 PVK and C 60 /PVK charge transfer complex was observed. The results indicated that the bonds between PVK chain and fullerene cages are easily broken under laser interaction and the fullerene cages ruptured from the chain are in active excited states favorable to the clustering of the clustering of the cages. The coalescence behavior of the C60/PVK mixture may be caused by the charge tranfer between fullerenes and PVK.