Suffrutines A (1) and B (2), a pair of novel photochemical Z/E isomeric indolizidine alkaloids, with a unique and highly conjugated C20 skeleton, were isolated from the roots of Flueggea suffruticosa. The structures were elucidated by extensive analysis of NMR spectra and single-crystal X-ray diffraction. The light-induced isomerization and hypothetical biogenetic pathway to 1 and 2, as well as their activity for regulating the morphology of Neuro-2a cells are also discussed. CI - (c) 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.