A series of four isostructural microporous coordination polymers (MCPs) differing in metal composition is demonstrated to exhibit exceptional uptake of CO2 at low pressures and ambient temperature. These conditions are particularly relevant for capture of flue gas from coal-fired power plants. A magnesium-based material is presented that is the highest surface area magnesium MCP yet reported and displays ultrahigh affinity based on heat of adsorption for CO2. This study demonstrates that physisorptive materials can achieve affinities and capacities competitive with amine sorbents while greatly reducing the energy cost associated with regeneration.