The synergistic effect of solid lubricants plays a significant role in wide-temperature-range lubrication, where the combination of lubricious oxide and Ag is the promising solid lubricants. In this paper, the friction and wear performances of Ni3Al with the addition of Ag and V2O5 solid-lubricating composites were evaluated from room temperature to 1000 °C. It was found that Ni3Al matrix composite with the addition of V2O5 has high friction coefficient of 0.3–0.7, while Ni3Al matrix composite with simultaneous addition of Ag and 2 wt % V2O5 has a relatively low friction coefficient of 0.25–0.4 between room temperature and 1000 °C and wear rate with the magnitude of 10−5 mm3/N m at high temperatures. The results revealed that nickel aluminum matrix solid-lubricating composite lubricated by silver and in situ formed silver vanadate at elevated temperature achieves a wide-temperature-range lubrication, which is attributed to the synergistic action of silver and silver vanadate formed at high temperatures.

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