The new nanoporous framework [Gd-4(di-nitro-BPDC)(4)(NO2)(3)(OH)(H2O)(5)] (solvent) (I; di-nitro-BPDC2- = 2,2'-dinitrobiphenyl-4,4'-dicarboxylate) has been designed and synthesized through a simple one-pot reaction. In addition to its exceptional thermal and water stabilities, I exhibited multifunctional properties. A sudden CO2 uptake to a maximum of 4.51 mmol g(-1) (195 K and 1 bar) with notable selectivity over O-2 and N-2 (CO2/O-2 = 39 at 195 K and 0.10 bar, CO2/N-2 = 46 at 195 K and 0.10 bar) and an isosteric adsorption enthalpy of 20.7(4) kJ mol(-1) have been revealed. Depending on the temperature and humidity, I also showed distinguished superprotonic conductivities with a maximum value and activation energy of 6.17 X 10(-2) S cm(-1) (55 degrees C, 99 RH%, and 1 V AC voltage) and 0.43 eV, respectively. With respect to the linear dependence of conductivities on both temperature (25-55 degrees C at 99 RH%) and humidity (55-99 RH% at 25 degrees C), the potential of I in temperature and humidity sensing was evaluated, disclosing an excellent sensing resolution and exceptional accuracy, precision, and repeatability for the measurements.