Hydrogen-sorption studies have been carried out for the catenation isomer pairs of PCN-6 and PCN-6′ (both have the formula of Cu3(TATB) 2, where TATB represents 4,4′,4″-s-triazine-2,4,6- triyltribenzoate with a formula of C24H12N 3O6). Inelastic neutron scattering (INS) studies reveal that the initial sites occupied by adsorbed H2 are the open Cu centers of the paddlewheel units with comparable interaction energies in the two isomers. At high H2 loadings, where the H2 molecules adsorb mainly on or around the organic linkers, the interaction is found to be substantially stronger in catenated PCN-6 than in noncatenated PCN-6′, leading to much higher H2 uptake in the isomer with catenation. Hydrogen sorption measurements at pressures up to 50 bar demonstrate that framework catenation can be favorable for the enhancement of hydrogen adsorption. For example, the excess hydrogen uptake of PCN-6 is 72 mg/g (6.7 wt %) at 77 K/50 bar or 9.3 mg/g (0.92 wt %) at 298 K/50 bar, respectively, and that for PCN-6′ is 42 mg/g (4.0 wt %) at 77 K/50 bar or 4.0 mg/g (0.40 wt %) at 298 K/50 bar. Importantly, PCN-6 exhibits a total hydrogen uptake of 95 mg/g (8.7 wt %) (corresponding to a total volumetric value of 53.0 g/L, estimated based on crystallographic density) at 77 K/50 bar and 15 mg/g (1.5 wt %) at 298 K/50 bar. Significantly, the expected usable capacity of PCN-6 is as high as 75 mg/g (or 41.9 g/L) at 77 K, if a recharging pressure of 1.5 bar is assumed.