Selective synthesis of silver and uniform single crystalline silver molybdate nanowires in large scale can be easily realized by a facile soft template approach. Ag6Mo10O33 nanowires with a uniform diameter of about 50 nm and the length up to several hundred micrometers were synthesized in large scale for the first time at room temperature using 12-silicotungstic acid system. The silver nanoparticles can be easily synthesized with the assistance of UV-light. Sensitive surfaceenhanced Raman scattering signals of p-aminothiophenol were observed on Ag nanoparticles and silver molybdate nanowires complex. The results demonstrated that synthetic method could be a potential mild way to selectively synthesize various molybdate nanowires with various phases in large scale. The silver nanoparticles and silver molybdate nanowires complex would be proposed for surface-enhanced Raman scattering substrate.