Catalytically activated carbon fibers and methods for their preparation are described. The activated carbon fibers are engineered to have a controlled porosity distribution that is readily optimized for specific applications using metal-containing nanoparticles as activation catalysts. The activated carbon fibers may be used in all manner of devices that contain carbon materials, including but not limited to various electrochemical devices (e.g., capacitors, batteries, fuel cells, and the like), hydrogen storage devices, filtration devices, catalytic substrates, and the like.