Topochemical synthesis of gold nanoparticles (AuNPs) was achieved on crystalline cellulose single nanofibers (CSNFs), which were tailored from native cellulose. Exposed AuNPs@CSNFs composite exhibited an excellent catalytic efficiency: the turnover frequency of the AuNPs@CSNFs was up to 840 times that of conventional polymer-supported AuNPs, for a model aqueous reduction reaction. Our novel strategy provides a promising solution to realize efficient use of limited noble metals using natural bioresources.