Bioinspired materials have aroused great interest as their inherent biocompatible and structural characteristics have given rise to sustainable applications. In this work, we have reported the phase and morphology transformation of chitosan from crystalline nanofibrils into amorphous sheets for fabricating sustainable materials. Acetylation-induced aqueous dissolution of native chitosan nanofibrils affords water-soluble chitosan as a biopolymeric liquid. Water-soluble chitosan macromolecules self-aggregate into amorphous sheets on solidification, presenting an interesting way to inspire new structures of chitosan assemblies. Through control over gelation, lyophilization, and self-assembled confinement of water-soluble chitosan, we have fabricated novel chitosan materials including filaments, aerogels, microspheres, and plastics that are promising for sustainable use. Bioinspired materials: chitosan filaments, aerogels, microspheres, and plastics have been designed by transforming crystalline nanofibrils into amorphous sheets on solidification.