In this study, we tried to improve the oxidation resistance of Nb-12Si (wt%) alloys at 1200 °C or higher through pack cementation coatings. Nb-12Si (wt%) alloys were prepared by arc-melting under Ar atmosphere. When the alloys were coated using pack powder mixtures composed of Si, Al2O3 and NaF, two silicide layers composed of NbSi2 and Nb5Si3 phases were successfully produced on the substrate. The Si-pack coatings were performed with various heat treatment temperatures and time conditions. The microstructures and thickness changes of the coating layers were analyzed to determine the growth behaviors of the coating layer. The growth constant of 8.4 10–9 cm2/sec was obtained with a diffusion growth mode. In addition, in order to examine the resistance of the Si-pack coated alloys, isothermal static oxidation tests were performed at 1200 °C and higher temperatures. As a result, the oxidation resistance of the alloys was determined by protecting the surface of the alloys with silicide oxide layers formed by the silicide coatings. The uncoated specimens exhibited an abnormal weight increase due to the formation of Nb oxide. The coated specimen showed excellent oxidation resistance at 1200 °C for up to 12 hrs, while the previous reports on the same alloy verified oxidation resistance only up to 1100 °C. It appears that the excellent oxidation resistance is closely related to the NbSi2 coating layer thickness. The oxidation behaviors of the coating layers after the oxidation tests were discussed in terms of microstructural and phase analyses.