Chitosan (CTS) is considered to be a common biomacromolecule/poly-cationic compound containing the potential functional groups that can be utilized as a feedstock for novel materials. In this study, CTS/graphene oxide (CTS/GO, CG) mixtures were prepared at different conditions to confirm a suitable hydrogel formation, then applied to produce paper-like materials with various thickness via a simple casting method. As a result, the morphological structure finally yielded the paper-like materials (CG2 papers with varying numbers of casting times) with the layer-by-layer structures instead of the tightly-sticky paper-like structure (GO paper). Based on the possible interactions between the CTS molecules and GO nanosheets, the CG mixtures could also be determined by FTIR and Raman analysis; concomitantly, their thermal properties reach higher than that of the pure GO. Notably, the strong interactions and compatibility of the CTS molecules and GO nanosheets revealed good dispersion and interfacial adhesion, leading to significantly enhancing the mechanical properties of the CG2 paper-like materials with increasing number of casting times or compared to GO paper. Therefore, the CG2 paper-like materials with the various numbers of casting times fabricated in the present study can expose new approaches for the design and application of future foil/paper-like materials, as well as the desired thickness of these foil/paper-like materials can be controlled easily.