Si3N4 nanowires prepared from the carbothermal reduction of carbonaceous silica xerogels with metal salt additives usually contain a small amount of nanotubes. This paper is devoted to the investigation of the formation mechanism of the Si3N4 nanowires. As-prepared samples heated at 1300 degrees C for different reaction times ( 1, 5, 10, and 30 h) were characterized by X- ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, and energy-dispersive X- ray spectroscopy. The results showed that all the samples mainly consisted of nanowires, while their crystalline phases changed with the heating time. Nitrogen-doped silicon oxide nanowires were first produced via the vapor-liquid-solid process and then underwent a stepwise surface nitrogenization to silicon nitride. The suggested mechanism can easily explain the existence of nanotubes in the Si3N4 nanowires.