MCM-41 was calcined at 500, 560, 600 or 650 ℃. It was used as support for NiW catalysts of hydrodenitrogenation (HDN) for quinoline in order to investigate the influences of the MCM-41’s calcination temperature on the structure and the HDN performance of NiW catalysts. The NiW catalysts were characterized by XRD, N2 adsorptiondesorption, XPS, Raman, HRTEM and Py-IR techniques. The results showed that the surface area (SBET), the average pore diameter (Dp) and the pore volume (Vp) of the MCM-41 increased with increase of the MCM-41’s calcination temperature. The high SBET, Dp and Vp were beneficial for the high dispersion of W species, the formation of appropriate nature of W species and acid sites on the catalysts. The HDN activity followed the order of NiW-650≒NiW-600>NiW- 560>NiW-500, while the relative selectivity of HDN pathways was similar for all the catalysts.