In this study, the photochromic processes of 8-N,N-dimethylamino-2,2-dimethyl-2H-pyrano[3,2-d]chromen-5-one (1) and its derivatives (2, 3) are investigated with steady-state, temperature-dependent and time-resolved absorption and emission spectroscopy. The differences among compounds 1-3 lie in their various substituents anchored at the pyran moiety that is subject to the photoinduced ring-opening reaction. Compounds 1. and 2 exhibit salient photochromism with a very unique phenomenon, in which fluorescence is observed in 1. for both the ring-closed form (1-CF, lambda(max) approximate to 445 nm) and the ring-open form (1-OF, lambda(max) approximate to 650 nm in CH2Cl2). The yields of forward and reverse photochromism processes were determined to be 0.40 and 1.0% for 1. Along with fluorescence quantum yields of 9.5 x 10(-2) and 5.8 x 10(-3) for 1-CF and 1-OF, respectively, 1 enables fluorescence detection while it exhibits photochromism in both directions, that is, a photoinduced on/off fluorescence switch. An increase in on/off ratiometric fluorescence between I-OF and 1-CF can reach a factor of 4.0 upon excitation at the absorption isosbestic point. The activation energies for the ground-state OFtrans -> CF thermal bleaching processes were determined to be 58.2 and 54.8 kJ/mol, with frequency factors of 1.7 x 10(5) and 3.6 x 10(5) s(-1) for 1 and 2, respectively. Conversely, bromo-substituted 3 did not undergo photochromic reaction, as evidenced by the lack of changes in the absorption spectrum after a prolonged (2 h) 354 nm (0.2 W/cm(2)) photolysis, manifesting the fact that other relaxation processes, such as enhanced intersystem crossing, may govern the deactivation of 3 (3-CF) upon excitation.