Palladium chloride doped chitosan composite nanofibers were prepared by electrospinning with sodium polyacrylate (PAAS) as the co‐spinning agent. The composite nanofibers are subsequently treated at elevated temperature to improve their solvent resistance. The Pd (II) cations inside the composite nanofibers were reduced into uniform palladium nanoparticles (Pd NPs) with mean diameter of ~4.93 nm. These Pd NPs inside the chitosan composite nanofibers exhibited excellent catalytic activity for Heck reactions of aromatic iodides with alkenes with yields over 85%. Moreover, due to the fibrous structure, this novel fibrous palladium catalyst could be readily recovered by simple filtration and reused for 18 times without loss of initial catalytic activity. It was found that the reactants could readily diffuse from the reaction solution to the active Pd NPs inside the nanofibers and the products could departure from composite fibers into the reaction solution, while the Pd NPs were tightly restricted inside the chitosan composite nanofibers.