<p>Developing solid sorbents that combine mechanical robustness with strong CO₂ affinity under low-pressure and elevated-temperature conditions remains a major challenge for practical carbon capture. Here, we report a silane-engineered silica–polymer hybrid aerogel platform in which organosilanes are deposited onto a reinforced SiA framework to simultaneously strengthen the skeleton and regulate the interfacial organization of a PEI/Zn/ionic-liquid active phase. Among the silanes examined, vinyltriethoxysilane affords the largest mechanical enhancement, increasing the compressive strength of the aerogel from 2.14 to 5.32&#xa0;MPa (+ 148.6%) while preserving a porous network. After loading polyethyleneimine, zinc acetate, and [EMIm]Br, the APTES-derived sorbent, SiA–A(24)–PZI, exhibits the best CO₂ capture performance, reaching 2.95 mmol g⁻¹ (+ 31.7%) at 298&#xa0;K and 1&#xa0;bar, 2.05 mmol g⁻¹ at 50 mbar, and 1.61 mmol g⁻¹ at 343&#xa0;K and 30 mbar. Under simulated flue-gas conditions, it delivers a dynamic CO₂ capacity of 2.19 mmol g⁻¹ under dry breakthrough and 2.27 mmol g⁻¹ under humid breakthrough, while maintaining high CO₂/N₂ selectivity and stable cycling behavior. Toth-model fitting, Qst–uptake analysis, in situ DRIFTS, DFT calculations, and conversion-dependent diffusivity modeling collectively reveal two distinct adsorption regimes: APTES-derived sorbents are dominated by amine-rich chemisorption with cooperative stabilization of carbamate/bicarbonate-type intermediates, whereas VTES-derived sorbents show a stronger contribution from micropore-assisted adsorption. These results establish silane engineering as an effective strategy for coupling framework reinforcement, active-phase organization, and adsorption energetics in hybrid aerogel sorbents.</p>