Flexible and Porous Hydrogel Architectures for Next‐Generation Sensing Technologies

ABSTRACT Porous hydrogels that integrate mechanical compliance with controllable molecular transport are critical for emerging soft bioelectronic and biochemical sensing platforms but the role of pore‐forming strategy in governing transport behavior and interfacial stability for biosensing remains insufficiently resolved. In this work, PVA–PEGDA–SA composite hydrogels were engineered via two distinct fabrication routes—sucrose porogen leaching and electrospinning—to systematically examine how processing methodology dictates membrane architecture and transport performance. Porogen leaching produced microporous networks with characteristic pore size ranges of 10–20 µm, while electrospinning generated interconnected nanofibrous membranes with sub‐micrometre pores (0.2–0.4 µm). These structurally distinct architectures resulted in fundamentally different transport regimes. Leached membranes exhibited enhanced swelling and high‐flux diffusion pathways, whereas electrospun membranes imposed regulated molecular ingress, reduced nanoscale roughness, and improved mechanical stability. Chronoamperometric measurements of cortisol in phosphate buffer demonstrate that electrospun membranes significantly suppress baseline noise and non‐specific transport, enabling stable, concentration‐dependent analyte diffusion and improved antifouling behavior at low analyte concentrations. Importantly, the results reveal that fabrication route functions not merely as a structural modifier but as a transport‐regime design parameter governing hydrogel–electrode interface behavior. This study provides a mechanistic framework for tailoring hydrogel membranes for soft wearable sensors, saliva‐compatible diagnostics, and selective molecular monitoring applications.