A mixture of acylglucosylsterols was isolated from the green fruits of Momordica charantia (balsam pear or bitter gourd) and the structure elucidated by high field 1H NMR, 13C NMR, FTIR and mass spectrometry and chemical modification studies followed by spectral and chromatographic analysis. The major acylglucosyl sterol was 3-O-[6′-O-palmitoyl-β-d-glucosyl]-stigmasta-5,25(27)-diene while the minor component was 3-O-[6′-O-stearyl-β-d-glucosyl]-stigmasta-5,25(27)-diene. The isolation and structure elucidation of these acylglucosyl sterols are reported for the first time.