Chemisorbent materials, based on porous aminosilicas, are among the most promising adsorbents for direct air capture applications, one of the key technologies to mitigate carbon emissions. Herein, a critical survey of all reported chemisorbed CO2 species, which may form in aminosilica surfaces, is performed by revisiting and providing new experimental proofs of assignment of the distinct CO2 species reported thus far in the literature, highlighting controversial assignments regarding the existence of chemisorbed CO2 species still under debate. Models of carbamic acid, alkylammonium carbamate with different conformations and hydrogen bonding arrangements were ascertained using density functional theory (DFT) methods, mainly through the comparison of the experimental 13C and 15N NMR chemical shifts with those obtained computationally. CO2 models with variable number of amines and silanol groups were also evaluated to explain the effect of amine aggregation in CO2 speciation under confinement. In addition, other less commonly studied chemisorbed CO2 species (e.g., alkylammonium bicarbonate, ditethered carbamic acid and silylpropylcarbamate), largely due to the difficulty in obtaining spectroscopic identification for those, have also been investigated in great detail. The existence of either neutral or charged (alkylammonium siloxides) amine groups, prior to CO2 adsorption, is also addressed. This work extends the molecular-level understanding of chemisorbed CO2 species in amine-oxide hybrid surfaces showing the benefit of integrating spectroscopy and theoretical approaches.