A new acylated anthocyanin was isolated from the purple-red flowers of Lobelia erinus cv 'Rosamond'. Its structure was elucidated to be cyanidin 3-O-(6-0-(4-O-trans-p-coumaryl-alpha-L-rhamnopyranosyl) -beta-D-glucopyranoside)-5-O-(6-O-malonyl-beta-D-glucopyranoside)-3'-O(6-O-trans-caffeyl-beta-D-glucopyranoside) by spectroscopic evidence. The three dimensional structure of this pigment was suggested from the observation of difference negative NOE spectrum analysis that cyanidin (chromophore) and caffeic acid (intracopigment) occupy a folding conformation as a stacking structure.