Fluorescent photoaffinity probe, which possesses a dansyl amide functional group on the maleic moiety of tautomycin, was prepared in order to detect the trace amount of labeled peptides. The parent compound dramatically showed fluorescence quenching before the photoreaction due to the exciplex formation on the basis of the folded conformation. Several benzhydrol analogs, on the other hand, recovered the Strong fluorescence; thus, this system could be employed for the photoaffinity labeling studies.