The incorporation of a chemo-responsive hydrogel into a 1D photonic porous silicon (PSi) transducer is demonstrated. A versatile hydrogel backbone is designed via the synthesis of an amine-functionalized polyacrylamide copolymer where further amine-specific biochemical reactions can enable control of cross-links between copolymer chains based on complementary target–probe systems. As an initial demonstration, the incorporation of disulfide chemistry to control cross-linking of this hydrogel system within a PSi Bragg mirror sensor is reported. Direct optical monitoring of a characteristic peak in the white light reflectivity spectrum of the incorporated PSi Bragg mirror facilitates real-time detection of the hydrogel dissolution in response to the target analyte (reducing agent) over a timescale of minutes. The hybrid sensor response characteristics are shown to systematically depend on hydrogel cross-linking density and applied target analyte concentration. Additionally, effects due to responsive hydrogel confinement in a porous template are shown to depend on pore size and architecture of the PSi transducer substrate. Sufficient copolymer and water is removed from the PSi transducer upon dissolution and drying of the hydrogel to induce color changes that can be detected by the unaided eye. This highlights the potential for future development for point-of-care diagnostic biosensing.