We have developed a technique by which poling and ion implantation in solid state are simultaneously accomplished. The technique has been applied to 2Ag2O∙3Na2O∙25ZnO∙70TeO2 (in mol %) glass. The glass is sandwiched by two cover glasses containing Na+ and then the thermal poling is carried out. We have accidentally found that Ag nanoparticles are selectively precipitated in the vicinity of the anode-side glass surface. X-ray photoelectron spectroscopy reveals that the glass composition of the anode-side glass surface becomes rich in Na+ after the thermal poling, which is caused by the Na+ implantation from the cover glass at the anode side.