AbstractA hydrophilic glycopolyamide homopolymer is described, consisting of a tertiary polyamide backbone and D‐glucose side chains, which upon direct dissolution in water can self‐assemble into spherical vesicles and nanofibers. Based on TEM, SFM, and SAXS data, it is proposed that the nanofibers are hollow nanotubes with a cross‐sectional radius of about 3 nm and a wall thickness of about 1 nm. The wall should be constructed of chains forming a sheet through intermolecular hydrogen bonding between amide and glucose units, as evidenced by CD spectroscopy.magnified image