Upon photoexcitation of 4-(dimethylamino)benzonitrile (DMABN) in the polar solvent acetonitrile (MeCN), a methyl group is subtracted from the dimethylamino substituent, producing 4-(methylamino)benzonitrile (MABN). The fluorescence of this photoproduct MABN occurs in the same spectral range as that of the locally excited (LE) state of DMABN. As DMABN undergoes efficient fluorescence quenching in MeCN, leading to a decrease of the LE fluorescence yield by a factor of 290 at 25 degrees C, whereas MABN is not quenched at all, even small amounts of this photoproduct strongly increase the apparent contribution of the LE emission to the total dual fluorescence spectrum of DMABN. As a further consequence of the photoproduct formation, the nanosecond decay time, tau(1), in the double-exponential LE fluorescence decay of DMABN in MeCN increases in relative intensity as compared to its picosecond counterpart, tau(2), as the fluorescence lifetime of MABN is similar to the tau(1) decay time of DMABN. The presence of the photoproduct MABN therefore can lead to a misinterpretation of the kinetic data derived from photostationary and time-resolved fluorescence experiments with DMABN in polar solvents. Photoproducts are also observed with 4-(N-pyrrolidinyl)aminobenzonitrile (P5C) and 4-(N-piperidinyl)aminobenzonitrile (P6C) in MeCN. In the case of P5C, 4-cyano-N-phenylpyrrole (PP4C) is the main product, whereas photolysis of P6C produces 4-aminobenzonitrile (ABN), among other photoproducts. This photodegradation, leading to the appearance of multiexponential decays, likewise has a negative influence on the ICT and LE fluorescence spectra and fluorescence decays of P6C and P5C, again impairing the validity of the kinetic analysis of these data. The isosbestic (absorption) and isoemission (fluorescence) points encountered in the spectra of DMABN and P6C during photoirradiation indicate that at least one photoproduct is formed.