Chitosan grafting acrylic copolymer (CTS-g-AA) supported Nano palladium catalyst was obtained in this paper. Chitosan grafting acrylic copolymer (CTS-g-AA) was prepared firstly and palladium was supported on CTS-g-AA; then nano fibrous catalyst was gained via electrospinning technique. The title catalysts were characterized by TEM, SEM and IR, the diameter of nanofiber was about 70~200 nm, the size of metal particles were in a range of 10~40 nm, and palladium particles dispersed on nanofibers homogeneously. The catalyst was applied to catalyze α-octene hydrogenation in normal temperature and pressure. The results showed that the conversion of α-octene was 99%, and the yield of octane was 65% by double-metal catalyst.