N-acyl chitosans (such as N-acetylated, N-maleyl, and N-succinyl chitosan), which were synthesized in glycine chloride ([Gly]Cl)/water homogeneous system, were of better moisture-absorption and moisture-retention abilities than those from the traditional methods, even better than hyaluronic acid. Moreover, the new method overcame many shortcomings, such as long reaction time, gel formed during the process of reaction, and complex workup procedure. In addition, the new [Gly]Cl solvent system was of the low volatility and no corrosion compared with organic solvent, especially, could be repeatedly used. Therefore, an environmental friendly approach for the synthesis of N-acyl chitosan was provided. At the same time, the N-acetylated chitosan fibers by wet-spinning using N-acetylated chitosan-[Gly]Cl as spinning dope solution were firstly reported, and the fibers had smooth surface as well as round and compact structure. More to the point, the N-acetylated chitosan fibers directly prepared in this study were of excellent mechanical properties. (c) 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013