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An optical technique to study the longitudinal distribution of ions in a bunched ion beam circulating in a storage ring is presented. It is based on the arrival-time analysis of photons emitted after collisional excitation of residual gas molecules. The beam-induced fluorescence was investigated in the ultraviolet regime with a channeltron and in the visible region using a photomultiplier tube. Both were applied to investigate the longitudinal shape of bunched and electron-cooled 209Bi80+ ion beams at about 400 MeV/u in the experimental storage ring (ESR) at GSI Helmholtzzentrum fur Schwerionenforschung in Darmstadt, Germany. Bunch lengths were determined with an uncertainty of about 0.5 m using the UV-sensitive channeltron and with slightly lower accuracy from the photomultiplier data due to the slower transitions in the red region of the spectrum. The Gaussian shape of the longitudinal distribution of ions inside the bunch was confirmed. With the information of the transverse beam size that can be measured simultaneously by a newly installed ionization profile monitor (IPM) at the ESR, an accurate determination of the ion density in the bunched beam will be allowed.