The sessile drop method combined with contact heating procedure was applied for the investigation of high-temperature interaction between liquid Gd and Y2O3 substrate. Real-time behavior of Gd sample in flowing inert gas (Ar) atmosphere upon heating to and at temperature of 1362 °C was recorded using high-speed high-resolution CCD camera. The results evidenced that molten Gd wets Y2O3 substrate (the contact angle θ < 90°) immediately after melting of metal sample observed at T = 1324 °C (Tm = 1312 °C). During the first 3 min of the sessile drop test, the contact angle dropped from θ = 52° to θ = 24° and then stabilized at the final value of θf* = 33°. The solidified Gd/Y2O3 couple was subjected to structural characterization using optical microscopy, scanning electron microscopy coupled with x-ray energy-dispersive spectroscopy. The results evidenced that the wettability in the Gd/Y2O3 system has a reactive nature and the leading mechanism of the interaction between liquid Gd and Y2O3 is the dissolution of the ceramic in the liquid metal responsible for the formation of a deep crater in the substrate under the drop. Therefore, the final contact angle θf*, estimated from the side-view drop image, should be considered as an apparent value, compared to the more reliable value of θf = 70° measured on the cross section of the solidified couple.