We study the transient photophysical properties of a diarylethene with a carboxylic anchor group by a combination of steady-state and ultrafast emission and absorption spectroscopy. After excitation of the closed-ring form, fluorescence with a quantum yield of 10−5 is observed and separated into different spectro-temporal components. The S1 state of the closed-ring form shows a lifetime of 1.3 ps and decays mainly by internal conversion to the S0 state of this isomer. This vibrationally hot ground state cools on a time scale of 10 ps.