Purification of a CHCl3-soluble extract from seeds of the Mexican medicinal arborescent morning glory, Ipomoea intrapilosa, by means of preparative-scale recycling HPLC, yielded seven new resin glycosides, intrapilosins I-VII (1-7). Their structures were established through the interpretation of their NMR spectroscopic and FABMS data. All pentasaccharides were found to be macrolactones of the known operculinic acid A with different fatty acids esterifying the same positions: C-2 on the second rhamnose unit and C-3 and C-4 on the third rhamnose moiety. The lactonization site of the aglycon could be placed at C-2 of the second saccharide. The fatty acid components of 1-7 were identified as (+)-(2S)-methylbutanoic, octanoic (caprylic), dodecanoic (lauric), and trans-cinnamic. The less common (-)-(2R)-methylbutanoic acid was also isolated as one of the saponification-liberated residues from intrapilosin IV (4). The presence of the (2R)- and (2S)-methylbutanoyl enantiomers bonded to the same oligosaccharide core in intrapilosins IV (4) and V (5) represents an example of diastereoisomerism due to a chiral esterifying moiety in the resin glycoside mixtures of a morning glory species.