The colloidal gold superparticle (SP)/polypyrrole (PPy) core/shell composites were successfully prepared by oxidative polymerization of pyrrole monomer on the surface of poly(N-vinylpyrrolidone) (PVP)-grafted colloidal gold SPs. These core/shell composites showed strong catalytic activity and excellent stability. Control experiments indicated that the morphology and the thickness of PPy shell were controllable by adjusting the dosage of pyrrole monomer. Meaningfully, the resulting SP/PPy core/shell composites were quite stable in water, which could be stored for more than half a year without damaging their structures. As an example, we demonstrated the use of these composites as catalyst for the reduction of methylene blue (MB) dye with a reducing agent of sodium borohydride. The composites exhibited highly catalytic activity and long-term stability, implying promising applications of SP/PPy composites in catalysis.