Abstract Lighter-weight, high melting materials, such as chromium or vanadium, are of interest to replace Ni-based superalloys in certain high-temperature applications. Cr and V alloys are also being investigated as structural materials for nuclear fusion applications. The influence of V additions (0 to 20 at pct) to Cr was investigated by analyzing arc-melted alloy samples in the as-cast and annealed states. Samples were characterized by X-ray diffraction, scanning electron microscopy, density measurements, Raman spectroscopy, and wavelength-dispersive X-ray spectroscopy. Vickers hardness and nanoindentation tests were performed to investigate the ductilizing effect of V additions to Cr. The oxidation resistance was tested by quasi-isothermal exposures at 800 °C for up to 300 h in synthetic air. A paralinear law was used to describe the transition from the parabolically grown Cr 2 O 3 oxide scale on pure Cr to the linearly grown, mixed Cr 2 O 3 /CrVO 4 scale on Cr–xV alloys. In the analyzed oxide scales of the alloys, no low melting, carcinogenic V 2 O 5 was detected. While nitridation occurred below the oxide scale for pure Cr, no nitridation was present below the mixed oxide scale of the V > 5 at pct alloys.