Nanoparticle organic hybrid materials (NOHMs) have been proposed as excellent electrolytes for combined CO₂ capture and electrochemical conversion due to their conductive nature and chemical tunability. However, CO₂ capture behavior and transport properties of these electrolytes after CO₂ capture have not yet been studied. Here, we use a variety of nuclear magnetic resonance (NMR) techniques to explore the carbon speciation and transport properties of branched polyethylenimine (PEI) and PEI-grafted silica nanoparticles (denoted as NOHM-I-PEI) after CO₂ capture. Quantitative ¹³C NMR spectra collected at variable temperatures reveal that absorbed CO₂ exists as carbamates (RHNCOO^- or RR'NCOO^-) and carbonate/bicarbonate (CO₃^2-/HCO₃^-). The transport properties of PEI and NOHM-I-PEI studied using ¹H pulsed-field-gradient NMR, combined with molecular dynamics simulations, demonstrate that coulombic interactions between negatively and positively charged chains dominate in PEI, while the self-diffusion in NOHM-I-PEI is dominated by silica nanoparticles. These results provide strategies for selecting adsorbed forms of carbon for electrochemical reduction.