Studying the fluorescence decay of chromophores, either used as fluorescent labels to stain specific biomolecules or as photosensitizers to produce irreversible chemical or physico-chemical modifications on biological substrates, is being demonstrated to be a valuable method of investigating the interactions underlying a variety of phenomena. In fact, all possible primary steps in a photosensitized biological system are phenomena that may occur during the chromophore S1 lifetime and act as quenching mechanisms of the S1 state. Thus they can be identified, and the relative importance of the corresponding transient species quantitatively determined, with suitable techniques of time-resolved fluorescence spectroscopy. The examples discussed in this paper concern both tumor photosensitizing drugs, such as anthracyclines and porphyrins, and skin sensitizers (e.g. furocoumarins).