A new flavonol glycoside, 5,4′-dimethylkaempferol 3-O-β-D-(6″-α-L-rhamnopyranosyl)-glucopyranoside, together with three known compounds were isolated from the n-butanolic soluble fraction of underground and aerial parts of Linaria vulgaris Mill, collected on the territory of Moldova. The characterisation of these compounds was achieved by various chromatographic and spectroscopic methods (IR, UV, 13C-NMR, 1H-NMR and MS).