This work demonstrates that a model system of poly­(N-isopropylacrylamide) (PNIPAam) macroporous hydrogels, with tailored microstructures and comprising gold (Au) or silver (Ag) nanoparticles, display enhanced and tunable catalytic activity. These nanocomposites are prepared using polymer templates obtained from melt-processed cocontinuous polymer blends. The reaction rate, controlled by both hydrogel porosity and the PNIPAam lower critical solution temperature, increases by more than an order of magnitude as compared to nonporous gels, and is comparable to micro- or nanocarrier-based systems, with easier catalyst recovery. The fabrication process is scalable, and is compatible with broad choices of polymer blend, gel, and nanoparticle chemistries.