In the field of surface engineering, the use of self-lubricous coatings with the incorporation of vanadium represent a promising approach to reduce friction, thus contributing to the wear behavior. For vanadium containing hard coatings produced by means of thin film technology, the reduction in friction at elevated temperatures was repeatedly attributed to temperature-induced and tribo-oxidatively formed oxides which act as solid lubricant. Only very few studies focused on the tribological characteristics of vanadium containing arc sprayed coatings. In this study, the tribological characteristics of a vanadium containing iron-based arc sprayed deposit were investigated in dry sliding experiments under ambient conditions and different temperatures. Types of wear at the worn surfaces and counterparts were examined by means of electron microscopy and energy dispersive X-ray (EDX) spectroscopy. The speciation of vanadium in the superficial layer was determined using X-ray absorption near edge structure (XANES) spectroscopy. It was found that the vanadium-containing coating exhibited a distinctly reduction of the coefficient of friction above 450 °C which further decreased with increasing temperature. XANES spectroscopy indicated an increased oxidation state for the V component on the coating surface, suggesting the prevalence of specific vanadium oxides which promote a self-lubricating ability of the coating