Nitrogen-doped carbon microfibers (N-CMFs) with porous textures have been synthesized by means of a floating catalyst chemical vapor deposition (FCCVD) with anhydrous ferric chloride as a catalyst precursor and melamine as both the carbon and nitrogen source. X-ray photoelectron spectroscope (XPS) characterization of the as-prepared N-CNFs reveals nitrogen atoms in the N-CMFs are mainly in the form of pyridine-like nitrogen and graphitic nitrogen. The sublimation and subsequent gas phase reduction of FeCl3 in H2 produces Fe micro-particles with high catalytic activity that leads to the growth of the microfibers. The electrochemical studies have shown that N-CMFs have a larger capacitance than the pure CMFs, showing promise for use as electrode materials in supercapacitors.