Four flavonol glycosides isolated from non-flowering leafy shoots of Iberis saxatilis (Brassicaceae) were characterised by spectroscopic and chemical methods as saxatilisins A–D, the 3-O-β-d-glucopyranosyl-(1→3)-α-l-rhamnopyranosyl-(1→2)[β-d-glucopyranosyl-(1→2)-α-l-rhamnopyranosyl-(1→6)]-β-d-glucopyranoside, 3-O-β-d-glucopyranosyl-(1→3)-α-l-rhamnopyranosyl-(1→2)[α-l-rhamnopyranosyl-(1→6)]-β-d-glucopyranoside, 3-O-(6-O-E-sinapoyl)-β-d-glucopyranosyl-(1→3)-α-l-rhamnopyranosyl-(1→2)[β-d-glucopyranosyl-(1→2)-α-l-rhamnopyranosyl-(1→6)]-β-d-glucopyranoside, and 3-O-(6-O-E-feruloyl)-β-d-glucopyranosyl-(1→3)-α-l-rhamnopyranosyl-(1→2)[β-d-glucopyranosyl-(1→2)-α-l-rhamnopyranosyl-(1→6)]-β-d-glucopyranoside of isorhamnetin (3,5,7,4′-tetrahydroxy-3′-methoxyflavone), respectively. Analysis of 2 J HC correlations detected with the H2BC (heteronuclear two-bond correlation) pulse sequence aided the unambiguous assignment of glycosidic resonances in the 1 H and 13 C NMR spectra of these compounds. Saxatilisins A, C, and D, are the first flavonol glycosides to be described with a pentasaccharide chain at a single glycosylation site. Several pentaglycosides of kaempferol and quercetin, tentatively assigned as saxatilisin analogues from LC–MS/MS analyses, were present as minor constituents of the extracts.