Silver nanoparticles (Ag NPs) with a mean size of about 90 nm were synthesized by polyol reduction of silver nitrate with ethylene glycol (EG) in the presence of poly(vinyl pyrrolidone) (PVP). The Ag NPs undergo a spontaneous coalescence in the presence of chloride ions even without a traditional sintering process which occurs at a relatively high temperature. Such behavior can cause a rapid decrease in the resistivity of the patterns fabricated by Ag NPs. Conductive silver lines were successfully fabricated on FR-4 substrate using this method. The resulting conductivity of the silver lines reached about 16% of the bulk silver value, which enables fabrication of conductive patterns on some electronic devices.