Two novel, triphenylamine derivatives N-(4-(4-(diphenylamino)styryl)phenyl)acetamide and N-(4-(4-(bis-(4-(4-(diphenyl-amino)styryl)phenyl)amino)styryl)phenyl)acetamide were synthesized. The two-photon absorption of N-(4-(4-(bis-(4-(4-(diphenyl-amino)styryl)phenyl)amino)styryl)phenyl) was ∼17-fold greater relative to N-(4-(4-(diphenylamino)styryl)phenyl)acetamide. Linear absorption spectra, steady-fluorescence and time-resolved fluorescence spectra revealed that electron coupling originating from π-electron delocalization is responsible for the strong cooperative enhancement of TPA within the compounds. This is confirmed by the Lippert-Mataga equation.