alpha-Si3N4 whiskers with novel saw-toothed and riblike structures have been synthesized in a high yield by a carbothermal reduction and nitridation route. The products were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), transmission electron microscopy (TEM), and selected-area electron diffraction (SAED). The results show that the saw-toothed whiskers with one smooth surface and another toothlike surface have lengths about several tens of microns and widths in the range of 600-1200 nm. The riblike whiskers are composed of Si3N4 rod-arrays, which grow closely packed perpendicular to the central axial whiskers with uniform diameter and length. The growth mechanism of the products can be considered as a combination of VS mechanism and secondary epitaxial nucleation process. The photoluminescence (PL) spectrum of the whiskers shows a strong blue light emission peak at 406 nm and a weak peak at 485 nm, suggesting their potential applications in light and electron emission devices.