Two crystalline beryllium carboxylates, Be2(OH)2(bdc) (BCF-3) and Be4(OH)4(btec) (BCF-4), have been prepared under hydrothermal conditions. BCF-3 has a novel zeolitic topology containing 3-ring and 14-ring windows. BCF-4 has a porous framework with a CO2 uptake capacity of 48.2 cm3 g−1 (298 K, 760 Torr).