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The Cu-Ni system is a typical dissolutive system due to its mutual dissolution across a wide range of temperatures and compositions. We characterized the effects of Ni dissolution on the wetting behavior of liquid Cu by combining high-temperature wetting experiments, in-situ observation of spreading and solidification, microstructure analysis of the quenched droplets, and computational fluid dynamic (CFD) simulations. In the very early moment, at 1100 °C, when the Cu droplet is brought in contact with the Ni substrate, it oscillates due to capillarity and is dampened by inertial effects, while the significant Ni dissolution at 1150 °C largely reduced the initial oscillations. Later, a peculiar spreading behavior is observed and we propose to describe it through a 4-step mechanism: pinning of the contact line by a newly formed solid solution layer at the interface acting as a physical barrier, driving of liquid towards the solidified edge due to a Ni-concentration induced Marangoni flow, forming of a precursor film ahead of the solidified edge caused by the strong Cu-Ni interactions and Marangoni flow, and finally depinning due to overflow as a result of liquid accumulation at the solidified edge. The formation of a solid solution layer is confirmed by in-situ observation and quenching. The Ni-concentration induced Marangoni flow is characterized experimentally and further investigated by CFD simulations. The proposed step flow mechanism can be potentially relevant to other dissolutive wetting systems (e.g. Bi/Sn, Ag/Cu and Cu/Fe systems), which are crucial for high-temperature processing techniques. [Display omitted] [ABSTRACT FROM AUTHOR]