Here, we demonstrate that water, in the superheated state, is a solvent for polyamide 4,6 (PA4,6) and that the water molecules can strongly influence hydrogen bonding. In the presence of superheated water, the melting temperature of PA4,6 can be suppressed by nearly 100°C. The depression in the melting temperature follows the Flory-Huggins principle. The instantaneous dissolution of the polymer hardly influences the molar mass of the polymer. However, if the polymer is retained in solution above the dissolution temperature for more than 10 min, hydrolysis occurs. These findings suggest that the dissolution of the aliphatic polymer in superheated water is mainly a physical process as opposed to a chemical process. Time resolved X-ray studies show that the dissolution occurs prior to the Brill transition temperature, as reported earlier. 1 Crystals grown from the water solution show a lath-like morphology with interchain and intersheet distances that are similar to the distances obtained for crystals grown from other known solvents.2,3 Electron diffraction further confirmed that the crystals grown from superheated water are single crystals, where the chains are perpendicular to the ab-plane. SAXS performed on dried sedimented water grown single crystals showed a lamellar thickness of 6 nm. The lamellar thickness is in accordance with other reported studies2 on PA4,6, confirming that the single crystals incorporate four repeat units between re-entrant folds with an amide group incorporated in the tight fold. Solid state NMR studies performed on mats of these single crystals showed two different mobilities of the proton associated with the amide groups: a higher mobility linked to the amide protons in the fold and a reduced mobility of the hydrogen bonded amide protons within the crystal. Additionally, the solid state NMR studies on the dried water crystallized single crystals show the presence of water molecule(s) in the vicinity of the amide groups. This was confirmed by infrared studies that conclusively demonstrated the appearance of two new bands arising due to the binding of a water molecule in the vicinity of the amide group (i.e., NH3+ and COO- bands that disappear upon heating at ∼200°C). Additionally, DSC traces of the water crystallized PA4,6 show an exothermic event in the same temperature region (i.e., in the vicinity of the Brill transition temperature, where the bound water exits from the lattice). Furthermore, this event was corroborated by TGA data. © 2008 American Chemical Society.