Poly[2-(acetoacetoxy) ethyl methacrylate] (PAEMA) homopolymers; were found to self-assemble into hierarchical superstructures, that is, double-stranded helical tubes of either screw sense (scanning force microscopy). Both the diameter and the pitch of the superhelices are similar to12 nm, and their length is 200-500 nm. It is proposed that PAEMA chains first organize into ribbons, the width of which determines the pitch of the helix, and then coil up into the helical superstructure. The formation of these structures is driven by the establishment of hydrogen-bridging interactions between adjacent acetoacetoxy groups (NMR and dielectric relaxation spectroscopy) and compensation of dipole moments.