The relaxation properties of the lowest excited states of singlet and triplet multiplicity of some photochromes with dipyrrolylperfluorocyclopentene structure have been investigated by conventional and time-resolved spectrometric techniques. These compounds can be photocoloured with a fairly high quantum yield (Phi(PC) >= 0.5). The bleaching is thermal and photochemical. The fluorescence emission is scarceor undetectable. No triplet absorption was observed by laser flash photolysis, whereas transients unaffected by oxygen (lifetimes in the range 60 ns-10 mu s) were detected beside the metastable closed form.