In this work, poly(styrene)@poly(N-isopropylmethacrylamide-co-2-(N,N-dimethyl)aminoethyl methacrylate [p(sty)@p(NIPMAM-DMAEMA)] core/shell microgel particles were produced by a two-step free-radical precipitation polymerization process. Ag nanoparticles were successfully embedded inside the sieves of a crosslinked network by using silver nitrate as the precursor salt and NaBH4 as the reductant. The synthesized pure and hybrid microgels were analyzed by various characterization tools, including Fourier transform infrared (FTIR) and UV-visible (UV-vis) spectroscopies, transmission electron microscopy (TEM) and dynamic light scattering (DLS). Results indicate the successful fabrication of spherical silver nanoparticles with diameters ranging from 10 to 15 nm within the sieves of the poly(styrene)@poly(N-isopropylmethacrylamide-co-2-(N,N-dimethyl)aminoethyl methacrylate) core/shell microgels, which have a hydrodynamic diameter of 155 ± 25 nm. The Ag nanomaterial exhibited long-term stability in the p(sty)@p(NIPMAM-DMAEMA) system due to the strong donor-acceptor relationship between the lone pair of the amide moiety in the polymer microgels and the Ag nanomaterial. The catalytic activity of the Ag-p(sty)@p(NIPMAM-DMAEMA) material was determined by performing the catalytic reduction of p-nitrophenol (4-NPh) as a model reaction under diverse concentrations of the catalyst. UV-vis spectrophotometry was used to check the progress of the reaction. The apparent rate constant (k app) was measured by applying the pseudo-first-order kinetics model. It was observed that k app increased with increasing catalyst dose, demonstrating occurrence of the reaction on the surface of the catalyst.