In reactive wetting aluminum (Al)/nickel (Ni) systems, oxides at liquid/gas (L/G) interfaces received less attention compared to intermetallic compounds forming at liquid Al/solid Ni interfaces yet potentially significantly influencing wetting properties. Between 900 and 1250 °C, we observed that the shape of sessile Al droplets with dense oxides at the L/G interface and intense interactions at liquid Al/solid Ni interfaces deviates from a spherical cap and can be used as a way to characterize the oxide evolution. This approach reveals a critical temperature of 1100 °C under a PO2 level of 3.9 × 10−9 atm and a vacuum level of ∼2 × 10−2 mbar. Above it, Al2O3 oxides at the L/G interface are eliminated as Al2O gas, while at lower temperatures, they develop as a mixture of Al2O3 oxides and Al-Ni intermetallic compounds with Ni being dissolved from the substrate. At high temperatures (above 1200 °C), despite oxide-free L/G interfaces, non-spherical cap shapes were also obtained due to the formation of sharp edges at the contact line triggered by the growth of intermetallic compounds. The coupling between the droplet shapes and the interfacial interactions is further confirmed by in-situ observation of oxides, analysis of quenched samples and thermodynamic calculations. The proposed method can be potentially applied to multiple reactive wetting systems (e.g. Sn/Cu, Al/Fe, Mg/Ni systems), which are crucial for high-temperature processes such as soldering, coating, and processing of metal matrix composites.