In the race for viable solutions that could slow down carbon emissions and help in meeting the climate change targets a lot of effort is being made towards the development of suitable CO₂ adsorbents with high surface area, tunable pore size and surface functionalities that could enhance selective adsorption. Here, we explored the use of silsesquioxane pillared graphene oxide for CO₂ capture; we modified silsesquioxane loading and processing parameters in order to obtain pillared structures with nanopores of the tailored size and surface properties to maximize the CO₂ sorption capacity. Powder X-ray diffraction, XPS and FTIR spectroscopies, thermal analysis (DTA/TGA), surface area measurements and CO₂ adsorption measurements were employed to characterize the materials and evaluate their performance. Through this optimisation process, materials with good CO₂ storage capacities of up to 1.7/1.5 mmol g⁻¹ at 273 K/298 K in atmospheric pressure, were achieved.