A particulate form carbon pyrolyzate adsorbent, having the following characteristics: (a) CO2 capacity greater than 105 cc/gram at one bar pressure and temperature of 273° Kelvin; (b) CO2 Working Capacity greater than 7.0 weight percent; (c) CO2 heats of adsorption and desorption each of which is in a range of from 10 to 50 kJ/mole; and (d) a CO2/N2 Henry's Law Separation Factor greater than 5. The carbon pyrolyzate material can be formed from a polyvinylidene chloride-based polymer or copolymer, or other suitable resin material, to provide an adsorbent that is useful for carbon dioxide capture applications, e.g., in treatment of flue gases from coal-fired power generation plants.