The electronic spectra of a number of benzylidene derivatives of N-aminoarylpyridinium perchlorates are associated with absorption localized on the individual pyridinium and azomethine fragments and with intramolecular charge transfer (ICT) from the azomethine fragment to the pyridinium ring. The luminescence is associated with the latter process. The photochromism is due to proton transfer in the excited state of the azomethine fragment, which competes with ICT, and is also due to structural factors.