The development of new derivatives based on renewable natural resources using green chemistry is a concept gaining recognition in several industries. This work focused on the preparation and characterization of cellulose carbonate using dimethyl carbonate as the green reagent in ethanoic KOH solution. The effect of several reaction parameters were evaluated, i.e., temperature (25°C, 50°C, 90°C, 120°C, 150°C, and 180°C), time (6, 24, 48, and 72h), KOH concentration (15% and 30%), and the use of a catalyst (DBU). The degree of substitution (DS) of the resulting materials was evaluated by 13C CP/MAS NMR. The spectra of the prepared cellulose carbonate exhibited the main peaks associated with cellulose macromolecules (C1-C6) and those corresponding to carbonate functions at approximately 162ppm. Moreover, XPS was performed and confirmed the reaction modifications. Nevertheless, it is worth noting that 13C NMR and XPS spectra showed a significant difference in DS value, due to the difference between both techniques. However, our results from NMR and XPS experiments confirm that the major modifications during all the reactions occurred mainly at the surface. This green process opens the way for the easy production of a new class of cellulose derivatives.