Five nitrogen sources (glycine, β‐alanine, urea, melamine and nicotinamide) and three heating methods (thermal, monomodal microwave and multimodal microwave) are used to prepare nitrogen‐doped Starbons® derived from starch. The materials are initially produced at 250–300 oC (SNx300y), then heated in vacuo to 800 oC to produce nitrogen‐doped SNx800y’s. Melamine gives the highest nitrogen incorporation without destroying the Starbon® pore structure and the microwave heating methods give higher nitrogen incorporations than thermal heating. The carbon dioxide adsorption capacities of the nitrogen‐doped Starbons® determined gravimetrically, in many cases exceed those of S300 and S800. The carbon dioxide, nitrogen and methane adsorption isotherms of the most promising materials are measured volumetrically. Most of the nitrogen‐doped materials show higher carbon dioxide adsorption capacities than S800, but lower methane and nitrogen adsorption capacities. As a result, the nitrogen‐doped Starbons® exhibit significantly enhanced carbon dioxide versus nitrogen and methane versus nitrogen selectivities compared to S800.