Porous carbon materials with pore sizes from 3 to 200 nm were synthesized by reacting hexafluorobenzene with Na liquid at 623 K. NaF crystals, a byproduct formed in the reaction, acted as nanotemplate to assist the pore formation. By employing hexafluorobenzene to react with Na incorporated within the channels (diameter 200 nm) of anodized aluminum oxide (AAO) membranes at 323-623 K, the carbon material can be fabricated into aligned porous nanotube arrays (ca. 250 nm in diameter, ca. 20 nm in wall thickness, ca. 0.06 mm in length, and ca. 3-90 nm in pore diameter). These materials were characterized by X-ray diffraction, scanning and transmission electron microscopy, X-ray energy dispersive spectroscopy, electron diffraction, thermal gravimetric analysis, and nitrogen physical adsorption experiments.