Four flavone glycosides isolated from extracts of the leaves of Robinia pseudoacacia (Leguminosae) were characterised by spectroscopic and chemical methods as the 7- O-β- d-glucuronopyranosyl-(1 → 2)[α- l-rhamnopyranosyl-(1 → 6)]-β- d-glucopyranosides of acacetin (5,7-dihydroxy-4′-methoxyflavone), apigenin (5,7,4′-trihydroxyflavone), diosmetin (5,7,3′-trihydroxy-4′-methoxyflavone) and luteolin (5,7,3′,4′-tetrahydroxyflavone). Assignment of glycosidic 1H and 13C resonances in their NMR spectra was facilitated by 2 J HC correlations detected using the H2BC (heteronuclear two-bond correlation) pulse sequence. Spectroscopic analysis of two known triglycosides, acacetin 7- O-β- d-glucopyranosyl-(1 → 2)[α- l-rhamnopyranosyl-(1 → 6)]-β- d-glucopyranoside (previously unrecorded from this species) and acacetin 7- O-β- d-xylopyranosyl-(1 → 2)[α- l-rhamnopyranosyl-(1 → 6)]-β- d-glucopyranoside (‘acacetin trioside’), enabled inconsistencies in the literature relating to these structures to be resolved. Comparison of the flavonoid chemistry of leaves and flowers of R. pseudoacacia using LC–UV and LC–MS showed that flavone 7- O-glycosides, particularly of acacetin, predominated in the former, whereas the latter comprised mainly flavonol 3,7-di- O-glycosides, including several examples new to this species. Tissue dependent differences in flavonoid chemistry were also evident from the glycosylation patterns of the compounds.