A straightforward, economically viable, and green approach for the synthesis of well-stabilized Au/Ag bimetallic nanoparticles is described; this method uses nontoxic and renewable degraded pueraria starch (DPS) as a matrix and mild reaction conditions. The DPS acted as both a reducing agent and a capping agent for the bimetallic nanoparticles. Au/Ag bimetallic nanoparticles were successfully grown within the DPS matrixes, and the bimetallic structures were characterized using various methods, including high-resolution transmission electron microscopy, energy-dispersive X-ray, and X-ray diffraction. Moreover, it was shown that these DPS-capped Au/Ag bimetallic nanoparticles could function as catalysts for the reduction of 4-nitrophenol in the presence of NaBH4 and were more effective than Au or Ag monometallic nanoparticles.