The preparation of the Fe-Mo-Ni catalyst using the sol-gel method was investigated. In addition, the catalytic selective oxidations of p-xylene (PX) to terephthalaldehyde (TPAL) on the Fe-Mo-Ni catalyst were also investigated. The catalysts were characterized using thermal analysis, H2-temperature programmed reduction (H2-TPR), Fourier transform infrared spectra (FT-IR), and X-ray photoelectron spectrum (XPS). The additional of Ni improves the catalytic activity of the Fe-Mo catalyst on selective oxidations of PX to TPAL. The optimal additive amount of Ni is 5%. XPS analysis shows that the introduction of Ni changes the internal structure of the Fe-Mo catalyst improves catalytic performance.