TiSiN coatings have been prepared by reactive DC magnetron co-sputtering on Coming glass and carbon steel substrates, using Ti-Si targets, with a constant Si:Ti area ratio of 0.2. The flow rate of nitrogen has been varied from 1.6 to 7.0 sccm, for a fixed argon flow rate of 25.0 sccm. We present a study of structure (texture, crystallite size and microstrain), chemical composition, and mechanical properties of the coatings and their dependence on the argon/nitrogen ratio. Moreover, a study of the thermal stability of the coatings has been performed by means of thermal annealing under oxidizing conditions (air atmosphere) at 500 and 600 degrees C. Coatings with the smallest crystallite size (similar to 2 nm) present the highest hardness (26 GPa) and the best thermal stability.