A novel chitosan fiber core/gold shell structural organic-inorganic composite was presented via a facile and eco-friendly approach. The chitosan fiber and gold/chitosan composites were characterized with the assistance of scanning electron microscopy and transmission electron microscopy observations. The chitosan fibers used in this study were 50 nm to 5 microm in diameter and up to hundreds of micrometers in length. The gold shells were typically 20-50 nm in depth, and their lattice fringes obliquely intersecting at an angle of 60 degrees were displayed. The formation mechanism of the as-fabricated chitosan fiber core with gold as the shell structural composites was also schematically discussed.