A novel V2O5@PANI composite nanowires were prepared by simply stirring in sodium nitrate solution and in-situ chemical oxidation polymerization methods. The V2O5@PANI composite nanowires display excellent optical and electrochemical properties, such as multicolor ranging from black, pale yellow, light yellow to dark green, outstanding cycling stability for 1000 cycles and fast switching time of bleaching and coloration (1.5 and 2.3 s, respectively). These outstanding performances are attributed to the synergistic effect between PANI encapsulated and original V2O5 nanobelts. The study offer a new synthesis strategy for fabricating inorganic-organic composite materials in optical and electrochemical fields. The morphology and structure of the composite were characterized by scanning electron microscopy, high-resolution transmission electron microscopy and X-Ray photoelectron spectroscopy.