A carbon aerogel was obtained by carbonization of an organic aerogel prepared by sol-gel polymerization of resorcinol and formaldehyde in water. The carbon aerogel was then CO2 activated at 800 C to increase its surface area and widen its microporosity. Evolution of these parameters was followed by gas adsorption and small- and wide-angle X-ray scattering (SAXS and WAXS, respectively) with contrast variation by using dry and wet (immersion in benzene and m-xylene) samples. For the original carbon aerogel, the surface area, S-SAXS, obtained by SAXS, is larger than that obtained by gas adsorption (S-ads). The values become nearly the same as the degree of activation of the carbon aerogel increases. This feature is due to the widening of the narrow microporosity in the carbon aerogel as the degree of activation is increased. In addition, WAXS results show that the short-range spatial correlations into the assemblies of hydrocarbon molecules confined inside the micropores are different from those existing in the liquid phase.