9-Fluorenylidenemalononitrile (FDCN) or 1,1-diphenyl-2,2-dicyanoethylene ( DPCN ) reacted with 10-methyl-9,10-dihydroacridine (AcrH2) under irradiation (λ> 320 nm) to give couping products. In order to gain further insight into the mechanism of the photo-induced reaction, the photophysics of the reactions of FDCN or DPCN with AcrH2 have been investigated by using UV-vis spectroscopy, fluorescence spectroscopy,excitation spectroscopy and time-resolved fluorescence spectroscopy, respectively. The results show that FDCN or DPCNinteracts with AcrH2 in the ground states to form a charge transfer complex, which further reacts to give the coupling product upon irradiation.