Macroscopically long core/shell structured Ag/Ag2S coaxial nanowires and Ag2S nanowires have been fabricated using the solid-state ionics method for Ag nanowires, combined with a subsequent gas–solid reaction, and characterized at different spatial scales. The photoconductive properties of such samples are investigated by performing transport measurements with 532 nm laser illumination ON/OFF cycles under different bias. A significant change in the photoconductivity from negative to positive has been observed in the coaxial structured Ag/Ag2S nanowires when the Ag2S layer thickness increases to a certain level. Such behaviors are ascribed to two photoconductive mechanisms in the Ag core and the Ag2S shell, respectively. These results indicate a promising approach to fabricate nanoscale photoswitches with different dark resistances and photoinduced currents based on the Ag/Ag2S coaxial nanowires for various optoelectronic applications.