Porous carbons derived from castanea mollissima shell are prepared by a simple alkali activation method, and employed as metal-free catalysts for catalytic dehydrogenation of propane to propylene, exhibiting high catalytic performance. The chemical compositions and structural properties of the obtained carbon catalysts are characterized by XRD, SEM, TEM, XPS, TG, He-TPD, Raman spectroscopy and nitrogen sorption techniques, revealing the presence of rich micro-/meso-/macropores and numerous oxygenated functional groups. The catalytic results suggest that the porous carbons obtained by activation of castanea mollissima shell with KOH at 700 degrees C exhibit the best catalytic performance. And the porous structure with high surface area and abundant oxygen-containing groups of the carbon catalysts are responsible for the high catalytic performance. This catalyst is derived from biomass, has much low cost, and can be widely used in various reactions including propane dehydrogenation.