Aliphatic 22,12-polyurethane has been crystallized directly from the melt and isothermally at 105 degreesC from N,N-dimethylformamide to give chain-folded lamellae of thickness approximate to14 nm. The crystals have been investigated using X-ray diffraction, electron microscopy (imaging and diffraction), and computer modeling. The diffraction data was used to establish that the chains crystallize in a single-chain, triclinic unit cell, and the structure bears a strong resemblance to chain-folded lamellar crystals of even-even nylons. The results show that, even for a molecule with relatively long alkane segments, the hydrogen bonds exercise a controlling influence on the crystallization process and crystalline structure. Two models were investigated: one based on an analogy with nylon 6 6 and the other derived using molecular dynamics; they both turned out to be closely related. The model generated using molecular dynamics predicted localized rotations at the termini of the ester-amide coupled units. The resolution of the experimental data was not sufficient to clearly delineate between the two models, but the separate calculations do provide an estimate of the tolerances that can be accepted.