A family of highly porous homochiral, racemic, and meso metal-organic frameworks (MOFs) were synthesized based on a new elongated tetra-carboxylate ligand and the copper paddle-wheel building units. These MOFs exhibited remarkable catenation isomerism that is controlled by both chirality of the bridging ligand and the size of solvent molecules. The ability to manipulate framework interpenetration is key to future synthesis os mesoporous homochiral MOFs which hold great promise in heterogeneous asymmetric catalysis and chiral separations.