Display omitted Biogenic, sustainable two-dimensional architectures, such as films and nanopapers, have garnered considerable interest because of their low carbon footprint, biodegradability, advanced optical/mechanical characteristics, and diverse potential applications. Here, bio-based nanopapers with tailored characteristics were engineered by the electrostatic complexation of oppositely charged colloidal phosphorylated cellulose nanofibers (P-CNFs) and deacetylated chitin nanocrystals (ChNCs). The electrostatic interaction between anionic P-CNFs and cationic ChNCs enhanced the stretchability and water stability of the nanopapers. Correspondingly, they exhibited a wet tensile strength of 17.7 MPa after 24 h of water immersion. Furthermore, the nanopapers exhibited good thermal stability and excellent self-extinguishing behavior, triggered by both phosphorous and nitrogen. These features make the nanopapers sustainable and promising structures for application in advanced fields, such as optoelectronics.