Chlorophyll (Chi) d was assigned to an antenna pigment of red algae in 1943, but its presence and function in red algae have not been necessarily clear for a long time. In 1996, it was shown that Chi d functioned as a major antenna pigment in a peculiar oxygenic photosynthetic prokaryote, Acaryochloris marina, isolated as a symbiont of a colonial ascidian from coral reefs. This finding evoked the necessity for reexamination of the presence and function of Chi d in red algae. We found Chi d in methanol-extract from several marine red algae, and the relative content was high in one species, Ahnfeltiopsis flabelliformis. Absorption and fluorescence spectra, HPLC analysis, and NMR and mass spectroscopy characterized Chi d extracted from the red algal thalli, and those were essentially identical to those of Chi d isolated from A. marina. However, micro-spectrophotometric analysis suggested that Chi d was not an actual constituent of the red algae but came from epiphyte(s) attached to surface of red algal thalli.