The increasingly stringent environmental regulations worldwide demand the use of efficient methods for air purification. Moreover, the alarming effect of greenhouse gases on the world climate requires the removal and sequestration of large quantities of anthropogenic carbon dioxide (CO2). This work is contributed towards the development of efficient, amine-containing, lamellar structured silica adsorbents for CO2 removal. Seven different materials were prepared by impregnation of various amounts of PEI, over as synthesized, or partially extracted or calcined lamellar silica. Materials were characterized by powder XRD and SEM. CO2 adsorption capacity was measured by thermogravimetry. The effects of PEI loading, temperature, CO2 partial pressure and surface alkyl chains were investigated. PEI seems to be dispersed better in a consistent surface alkyl chain network, leading to enhanced CO2 uptake. VB-13, the material with 50 wt% of PEI, recorded the highest CO2 uptake at 75 °C, in the presence of both 15% CO2/N2 and 100% CO2 with values of 3.02 and 3.50 mmol/g respectively. The optimum temperature for CO2 uptake was found to be 75 °C for samples with high PEI loading. Moreover, higher uptake was recorded in the presence of 100% CO2 versus 15% CO2/N2 for all temperatures. Another objective of this study was to investigate the effect of humidity on the CO2 adsorption process. In that case use of the column-breakthrough technique coupled with mass spectrometry to discriminate between CO2 and water was considered. Complete understanding of the technique and the different effects of moisture on CO2 adsorption over amine-containing materials, namely promotion of CO2 uptake and stabilization of the adsorbent, were achieved, based on a thorough scrutiny of the literature. Nonetheless, because of the Covid-19 pandemic and several technical issues, some experiments could not be undertaken.