The hybrid ultraporous material TIFSIX-Ni ([Ni(pyrazine)2(TiF6)]n) was incorporated into a composite ink for the first time for the three-dimensional (3D) printing of monoliths. The large-scale synthesis of TIFSIX-Ni was completed using two different Ni(II) salts, with CO2uptakes of 1.90 mmol g–1achieved using mechanochemically assisted thermal synthesis. The monoliths were then tested for the capture and release of CO2gas using electric swing adsorption (ESA) under dry and humid conditions. A working capacity of 1.7% was achieved (comparing dynamic data with isotherm data) when a current of 2.1 A was applied for 10 min. The monolith could be cycled repeatedly for 6 h without impacting the performance of the material or loss of capacity. Part of this work explored the improvement of mechanochemically assisted synthetic methods of TIFISX-Ni in reducing the costs associated with large-scale production, allowing for improvements in the overall scale-up and processability of the material for industrial applications.