The tetrapyrrolic chlorophyll catabolites (or phyllobilins, PBs) were analyzed in yellow fall leaves of the grape Chardonnay, a common Vitis vinifera white wine cultivar. The major fractions in leaf extracts of V. vinifera, tentatively assigned to PBs, were isolated and their structures elucidated. The dominant fraction is a dioxobilin‐type non‐fluorescent Chl‐catabolite of a previously observed type. Two less polar fluorescent PBs were characterized as a novel dioxobilin‐type fluorescent Chl‐catabolite with a bicyclo‐1′,6′‐glycosyl architecture, and its new fluorescent formyloxobilin‐type analogue. The discovery of persistent hypermodified fluorescent PBs with the architecture of bicyclo‐[17.3.1]‐PBs (bcPBs), suggests the activity of an unknown enzyme that forges the 20‐membered macroring at the tetrapyrrolic core of a fluorescent PB. bcPBs may play specific physiological roles in grapevine plants and represent endogenous anti‐infective agents, as found similarly for other organic bicyclo‐[n.3.1]‐1′,6′‐glycosyl derivatives.