In this dissertation, we engineer the pores of inorganic and hybrid porous materials to produce novel stimuli-responsive degradable nanosystems for controlled release of cargos for biomedical applications. The design of biodegradable silica-iron oxide hybrid nanovectors with large mesopores for large protein delivery in cancer cells is described. The mesopores of the nanomaterials span 20 to 60 nm in diameter, and post-functionalization allowed the electrostatic immobilization of large proteins (e.g., mTFP-Ferritin, ~534 kDa). The presence of iron oxide nanophases allowed for the rapid biodegradation of the carrier in fetal bovine serum as well as magnetic responsiveness. The nanovectors released large protein cargos in aqueous solution under acidic pH or magnetic stimuli. The delivery of large proteins was then autonomously achieved in cancer cells via the silica-iron oxide nanovectors, which is thus very promising for biomedical applications.