The catalytic hydrogenation of 5-(3-hydroxypropyl)-1,2-dihydropyrrolizines gave a mixture of stereoisbmers of 3(5)-(3-hydroxypropyl)pyrrolizidines, which was separated successfully. The stereochemistry of the compounds obtained was determined by means of the IR and 13C NMR spectra. The presence of strong intramolecular hydrogen bonds was detected. The basicities of the compounds obtained were determined.