Kaempferol‐3‐O‐[6Glc‐O‐feruloyl]‐β‐D‐glucopyranosyl‐(1→2)‐O‐[α‐L‐rhamnopyranosyl‐(1→6)]‐β‐D‐galactopyranoside (1) was isolated from the aerial parts of Brunfelsia grandiflora ssp. grandiflora. The structure of this novel flavonol glycoside was established by fast atom bombardment‐mass spectrometry and by means of NMR spectroscopy at 14T, using two‐dimensional NMR experiments with pulsed‐field gradients for coherence selection. The presence of the constituent aglycones and sugar units of 1 was confirmed independently by acid hydrolysis.