The synthesis of carbonaceous materials with a high surface density of amino functions for CO2 sorption and sequestration is reported. The amino-rich carbonaceous materials are characterized by elemental analysis, N2 sorption, scanning and transmission electron microscopy, zeta potential, TGA and FTIR measurements. A detailed discussion on the use of these materials in CO2 capture is provided. The materials show significant sorption capabilities for CO2 (4.3 mmol g−1at −20 °C and 1 bar). Furthermore, they show a high apparent selectivity for CO2 over N2 at both low and high temperatures.