Visible light driven pollutant degradation by photocatalyst was one of most efficient and economical strategies for environmental application. The focus and challenge was to fabricate efficient artificial photocatalysts. In this work, hybrid Ag2CO3/AgVO3 nanowires were first reported to be successfully synthesized by the facile ion exchange method. The as-prepared Ag2CO3/AgVO3 nanowires showed highly improved visible light photo catalytic activity for RhB degradation, and the optimized Ag2CO3/AgVO3-40% photocatalyst exhibited the best photocatalytic activity, which is 3.6 times of pure Ag2CO3 and 13.3 times of pure AgVO3 catalysts, mainly due to the formation of Ag nanoparticles and Ag2CO3/AgVO3 heterojunction for charge separation. The degradation of RhB solution was mainly attributed to direct hole oxidation, which was also confirmed by the active species trapping experiments. Finally, the possible visible light photocatalytic mechanism of Ag/Ag2CO3/AgVO3 composites for RhB degradation was proposed.