This study explores the modification of pore structures in porous silica materials synthesized using sodium silicate and waste gelatin, under varying silica‐to‐gelatin ratios. At ratios of 1.0–1.5, bimodal porous silica with mesopores and macropores emerged due to spaces between silica nanoparticles and clusters, following gelatin elimination. The study further evaluated the obtained bimodal porous silica as polyethyleneimine (PEI) supports for CO2 capture, alongside PEI‐loaded unimodal porous silica and hollow silica sphere for comparison. Notably, the PEI‐loaded bimodal silica showcased superior CO2 uptake, achieving 145.6 mg g−1 at 90 °C. Transmission electron microscopy (TEM) revealed PEI′s uniform distribution within the pores of bimodal silica, unlike the excessive surface layering seen in unimodal silica. Conversely, PEI completely filled the hollow porous silica‘s interior, extending gas molecule diffusion distance. All sorbents displayed nearly constant CO2 adsorption across 20 cycles, demonstrating outstanding stability. Notably, the bimodal porous silica displayed a negligible capacity loss, underscoring its robust performance.