This chapter explores the design and synthesis of polysaccharide-based organic–inorganic hybrid systems for the encapsulation and controlled release of hydrophilic active ingredients in biomedical applications. By integrating biopolymers such as chitosan and alginate with silica nanostructures, the resulting materials achieve enhanced mechanical stability, biocompatibility, and tunable release profiles. Three main encapsulation strategies are detailed: (1) macroscopic hydrogel beads and scaffolds formed via ionotropic gelation, (2) microparticles prepared through spray drying, and (3) nanocapsules generated using inverse nanoemulsions. Each technique enables size-controlled encapsulation, with potential applications ranging from drug delivery to tissue engineering and catalysis. The incorporation of silica contributes to sustained release behavior and structural integrity across all scales. The chapter highlights the versatility and scalability of these hybrid systems, advocating for future developments such as hydrophobic drug loading and targeted delivery via surface functionalization.