The global warming impacts associated with anthropogenic CO2 emissions from fossil fuel combustion present an enduring problem to achieving energy sustainability. Although conservation measures and carbonless energy technologies may eventually stabilize CO2 emissions from stationary and mobile power sources, a continued reliance on coal, oil and natural gas in the near term necessitates development of strategies to reduce CO2 loadings into the atmosphere. Carbon capture and storage (CCS) is a promising concept in which CO2 is recovered from combustion stack gases, concentrated to a fraction suitable for pipeline transport, and sequestered in geologic formations or other storage media. Unmineable coal seams are particularly attractive host formations for geosequestration of CO2. Improved adsorbents are needed however for CO2 capture from flue gas, and the capacity of coalbed media must be evaluated for its long-term CO2 storage potential. In this paper, we report molecular simulation studies of CO2 adsorption on model coal macromolecules and metal-organic framework (MOF) adsorbents. Novel porous materials based on MOF chemistries show promise for selective capture of CO2 from post-combustion flue gas mixtures. Isotherms were generated via Monte Carlo simulation for CO2 adsorption at 273 K in 1.35-2.4 nm diameter pores with surface chemical and energetic heterogeneity characteristic of high rank coals. Point charges for surface oxygen groups were calculated using ab initio methods. Significant enhancement of CO2 uptake is found to occur at low pressure on the coal-like surface relative to a homogeneous graphite surface due to adsorbate interactions with surface oxygen groups. Selectivity of CO2/CH4 adsorption is reported and the effects of electrostatic interactions are discussed. Monte Carlo simulation results are also presented for CO2 adsorption in a copper-bipyridine MOF that exhibits highly selective gated adsorption for CO2.