Alcohol-containing polymer networks synthesized by Friedel–Crafts alkylation have surface areas of up to 1015 m2/g. Both racemic and chiral microporous binaphthol (BINOL) networks can be produced by a simple, one-step route. The BINOL networks show higher CO2 capture capacities than their naphthol counterparts under idealized, dry conditions. In the presence of water vapor, however, these BINOL networks adsorb less CO2 than more hydrophobic analogues, suggesting that idealized measurements may give a poor indication of performance under more realistic carbon capture conditions.