The outstanding potential of mesoporous carbonaceous materials [1] requires a methodology that grants control over their surface chemistry and the distribution of pore sizes. The best current method that achieves control over pore-size distribution is the templating method. A typical procedure [1c] involves filling mesoporous silica with a carbon precursor (e.g. sucrose), which is subsequently carbonized through a series of high-temperature processes. The template is then removed by using hydrofluoric acid or caustic soda. The resultant activated carbons produced by this method possess wellordered mesoporous structures with a large specific volume and physical properties amenable to a broad range of applications.[2] However, highly aggressive chemicals involved limit this approach to the production of stable graphitic carbons with inert hydrophobic surfaces. [3] To functionalize and open up new chemistry, further difficult chemical modifications are required. This is at the cost of reducing the availability of the mesopores.[4]Herein we report a novel approach for the generation of a new family of mesoporous carbonaceous materials with surfaces ranging from hydrophilic to hydrophobic, which is controlled by the degree of carbonization. The method utilizes the natural ability of the amylose and amylopectin polymer chains within the starch granules to assemble into an organized nanoscale lamellar structure, which consists of crystalline and amorphous regions.[5] Our strategy was to synthesize mesoporous carbons (hereinafter referred to as "starbons") by using mesoporous expanded starch [6] as the precursor without the need for a templating agent. This process is gentle and provides the opportunity to produce a whole range of mesoporous carbon-based materials from starch to activated carbon, including amorphous oxygencontaining carbons that have many applications, [7] such as catalysis, [7a, b] adsorption, [7c] and medicine, [7d, e] owing to their varied surface functionalities.The approach described is illustrated in Scheme 1. First, a simple process of gelatization in water opens up and disorders the dense biopolymer network, [8] after which it partially recrystallizes during a process of retrogradation.[9] Exchanging water with a lower-surface-tension solvent (usually ethanol) prevents collapse of the network structure during the drying process. After drying, the expanded mesoporous starch is obtained. In the final stage of the process, mesoporous starch is doped with a catalytic amount of organic acid (e.g. para-toluenesulfonic acid) and heated under vacuum. This enables fast carbonization and fixing of the mesoporous structure. Heating at different temperatures, ranging from 150 to 700 8C has produced a variety of mesoporous materials from amorphous carbons to graphite-like activated carbons. Native starch granules do not produce mesoporous materials when carbonized. This indicates that the formation of expanded starch as a precursor to starbon is crucial.