Selective CO2 adsorption over other small gases has been realized in an ultra-microporous metal–organic framework (MOF). In the quest of manifesting such selective carbon capture performance, the prefunctionalized linker strategy has been espoused. A new Zn(II)-based three-dimensional, 3-fold interpenetrated metal–organic framework material [Zn(PBDA)(DPNI)]n·xG (PBDA: 4,4′-((2-(tert-butyl)-1,4-phenylene)bis(oxy))dibenzoic acid; DPNI: N,N′-di(4-pyridyl)-1,4,5,8-naphthalenetetracarboxydiimide; xG: x number of guest species) with unusual rob topology is synthesized following a typical solvothermal synthesis protocol, which gleans a modest CO2-selective adsorption trend over its congener gases (saturation CO2 uptake capacity: 2.39 and 3.44 mmol g–1, at 298 and 273 K; volumetric single component isotherm based separation ratios at 0.2 bar: 189.4 (CO2/N2, 256.5 (CO2/H2), 12.3 (CO2/CH4); at 1 bar: 6.8 (CO2/N2, 17.1 (CO2/H2), 7.1 (CO2/CH4)). The compound also exhibits selective benzene sorption over its aliphatic...