A facile method was developed to prepare silica-silver core-shell composite microspheres with continuous, compact, and conductive silver layers. The procedure involves dopamine oxidative self-polymerization and electroless plating. The poly(dopamine) layer was used as the chemi-sorption sites for silver ions and promoted the silver deposition. The electroless plating procedure involves a combination of surface activation, seeding growth, and deposition. The chemical composition and the crystal structure of the silica-silver core-shell composite microspheres were studied by X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD), respectively. In addition, the surface morphology and chemical composition of each composite microsphere were confirmed by scanning electron microscopy and energy dispersive X-ray spectroscopy. The results demonstrated that the silver layer on the silica surface was continuous and compacted.