An expanded 4,4-paddlewheel-connected porous MOF-505-type metal-organic framework (MOF), [Cu-2(PDEB)(H2O)(2)].xS (NJU-Bail2; NJU-Bai represents the Nanjing University Bai group and S represents noncoordinated solvent molecules) has been designed from a nanosized rectangular diisophthalate linker containing alkyne groups 5,5'-(1,4-phenylenedi-2,1-ethynediyl)bis(1,3-benzenecarboxylic acid). This MOF material possesses permanent microporosity with the highest Brunauer-Emmett-Teller surface area of 3038 m(2).g(-1) and the largest unsaturated total hydrogen storage capacity of 62.7 mg.g(-1) at 77 K and 20 bar among reported MOF-505 analogues. Additionally, NJU-Bail2 also exhibits excellent carbon dioxide (CO2) uptake capacity (23.83 and 19.85 mmol.g(-1) at 20 bar for 273 and 298 K, respectively) and selective gas adsorption properties with CO2/CH4 selectivity of 5.0 and CO2/N-2 selectivity of 24.6 at room temperature.