Herein, we aim to fabricate nanoporous gyroid SiO2 from templated sol-gel reaction using degradable block copolymer with gyroid-forming nanostructure as a template and then to functionalize the nanoporous materials using "smart" polymer, poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA), brushes via the "grafting from" method to give double-stimuli-responsive properties. By taking advantage of the responses to environmental stimuli, both thermal and pH, the pore features can be well-defined by the stretching and recoiling of PDMAEMA brushes because of their adjustable chain conformations with reversible character. The responsive properties with respect to environmental stimuli can be successfully traced by temperature-resolved small-angle X-ray scattering (SAXS) in aqueous environment. Owing to the high specific surface area and porosity, 3D pore network, biocompatibility, and environmental responses, the functionalized nanoporous gyroid SiO2 is further demonstrated as a stimuli-responsive controlled release system.