Environmentally friendly and potentially bioactive food packaging based on chitosan-coated papers were elaborated. The morphology and the microstructure of these new materials were characterized by infrared spectroscopy and scanning electron microscopy. These observations suggested that the chitosan penetrated deeply into the paper, embedding the cellulose fibers, instead of forming a layer as expected. Through the barrier properties against moisture, the liquid water sensitivity, and NMR-relaxometry measurements, the water interactions were evaluated on the chitosan films and the chitosan-coated papers. They revealed that the coating by a chitosan film forming solution improved the paper moisture barrier properties but the surface hydrophilicity remained high. Relaxometry studies showed that, due to its hydrophilic character, chitosan controlled the interaction with water, despite the very low amount of deposit. On the other hand, the mechanical properties of papers were unmodified by the chitosan coating, which did not fundamentally affect the solid structure of the papers.