In this work, carbon papers and aerogels based on graphene layers and chitosan were prepared. They were obtained by mixing chitosan (CS) and a high surface area nanosized graphite (HSAG) in water in the presence of acetic acid. HSAG/CS water dispersions were stable for months. High resolution transmission electron microscopy revealed the presence of few graphene layers in water suspensions. Casting or lyophilization of such suspensions led to the preparation of carbon paper and aerogel, respectively. In X-ray spectra of both aerogels and carbon paper, peaks due to regular stacks of graphene layers were not detected: graphene with unaltered sp2 structure was obtained directly from graphite without the use of any chemical reaction. The composites were demonstrated to be electrically conductive thanks to the graphene. Chitosan thus makes it possible to obtain monolithic carbon aerogels and flexible and free-standing graphene papers directly from a nanosized graphite by avoiding oxidation to graphite oxide and successive reduction. Strong interaction between polycationic chitosan and the aromatic substrate appears to be at the origin of the stability of HSAG/CS adducts. Cation-π interaction is hypothesized, also on the basis of X-ray photoelectron spectroscopy findings. This work paves the way for the easy large-scale preparation of carbon papers through a method that has a low environmental impact and is based on a biosourced polymer, graphene, and water.