Molds made of tool steels used in aluminum high-pressure die casting should routinely withstand tens of thousands of injection cycles, but repeated loading and temperature spikes result in their frequent premature wear. Extending their lifetime could be sought by nitriding or application of coatings of even higher hardness or both. Therefore, in the present experiment the arc-deposited Cr/(CrN)/nx(CrN/CrAlN)/mx(CrAlN/VN) or Cr/(CrN)/nx(CrN/TiAlN)/mx(TiAlN/VN) nano-multilayer stacks were deposited on glow discharge nitrided X40CrMoV5.1 steel. The scanning and transmission electron microscopy backed by Energy Dispersive X-ray Spectroscopy measurements of local chemical composition helped to confirm that the coatings are built of nanolayers of respective nitrides of period less than 10 nm. They also showed that droplets being characteristic for arc deposition method were enriched either in chromium, aluminum or vanadium but not in titanium. Both coatings presented comparable hardness of ~25 GPa, but the one covered with TiAlN/VN was roughly twice as wear resistant as the CrAlN/VN. Simultaneously, they were ~200 and ~100 more wear resistant than X40CrMoV5.1reference steel.