In this work, the micro-textural properties of CaO-based CO2 sorbents prepared in a thermo-gravimetric reactor were investigated by ex situ synchrotron-based Small Angle X-ray Scattering (SAXS), Ultra Small Angle X-ray Scattering (USAXS) and Wide Angle X-ray Scattering (WAXS). Six sorbent samples were produced by calcination in vacuum at different temperatures and durations of the heating step; additionally, four partially carbonated samples were produced, after calcination in vacuum, at different CaO conversions. The scattering intensity profiles were analyzed by means of the Unified Fit model. Bimodal pore size distributions (micro-pores and meso-pores) were identified and the micro-textural properties (porosity, specific surface and pore radius of gyration) of each of the two pore populations were quantified both for the calcined and for the carbonated samples. The micro-textural properties of a few calcined samples were compared with N-2-adsorption measurements. For each pore population, the trends of porosity, specific surface and pore radius of gyration, in addition to the pore number density and sphericity factor, were obtained versus time during the calcination and versus the CaO conversion during the carbonation. The relevance of micro-pores with respect to macro-pores was assessed both as far as the porosity impact on the CO2 capture capacity and as far as the specific surface impact on the carbonation kinetics. For the calcined samples, the micro-textural properties of a partially calcined sample were compared with those of the completely calcined samples, and pore correlation distances were determined. For the carbonated samples, the specific surface per unit of particle volume results linearly dependent on the CaO conversion and, if expressed per unit of mass of unreacted CaO, does not change significantly for most of the CaO carbonation.