<p>Current polymerization strategies for CO₂ utilization are often constrained by harsh operating conditions, limited selectivity, and insufficient catalyst recyclability. A sustainable and cost-effective catalytic protocol is introduced for the synthesis of biopolymers and polymers from CO₂ with oxetane, epoxide, or limonene epoxide under mild conditions. The catalytic system is based on dendritic fibrous nanosilica (DFNS) functionalized with ionic liquids (ILs) containing CO₃²⁻ anions and imidazolium cations. The resulting DFNS–IL hybrid nanostructures provide highly accessible active sites and act as stable, recyclable heterogeneous catalysts, achieving yields up to 98% with excellent selectivity. The catalysts can be readily recovered and reused over multiple cycles without significant loss of activity. Structural and spectroscopic analyses confirm the successful immobilization of ionic liquids on DFNS and their critical role in enhancing CO₂-based polymerization. This approach demonstrates an environmentally benign and practical pathway for the valorization of CO₂ into value-added polymeric materials.</p>