Bismaleimides and bisitaconimides bearing diphenylmethylamine, triphenylamine, or 2,5-diphenyl-1,3,4-oxadiazole chromophore (symbolized as A(=)−D (*) −A(=)), as well as their saturated model compounds were synthesized, and their steady-state and time-resolved fluorescence spectra were investigated. These A(=)−D(*)−A(=) monomers display strong intramolecular fluorescence quenching. Their fluorescence quantum yields and lifetimes are generally lower than those of their model compounds. It was found that the electron-poor CC bond of maleimide and itaconimide units (A(=)) plays a key role in the intramolecular quenching, which is correlated to the electron-accepting ability of A(=) and the geometry arrangement between A(=) and electron-donating chromophore (D(*)). The intramolecular quenching was attributed to an intramolecular charge transfer interaction, which was confirmed by intermolecular fluorescence quenching and time-resolved fluorescence studies. On the basis of the intramolecular quenching, a new fluorescence approach can be developed to monitor the process of the polymerization and curing of bismaleimides, which can directly reflect the CC bond consumption during polymerization and curing. The new fluorescence approach can be utilized not only by an intrinsic fluorescence technique but also by an extrinsic fluorescence technique.