Wetting characteristics of the Al/ZrB 2 system were experimentally determined by the sessile drop method with application of separate heating of the ZrB 2 and Al samples and combined with in situ cleaning of Al drop from native oxide film directly in vacuum chamber. The tests were performed in ultrahigh vacuum of 10 26 mbar at temperatures 710, 800, and 900°C as well as in flowing inert gas (Ar) atmosphere at 1400°C. The results evidenced that liquid Al does not wet ZrB 2 substrate at 710 and 800°C, forming high contact angles (h) of 128°and 120°, respectively. At 900°C, wetting phenomenon (h < 90°) occurs in 29th minute and the contact angle decreases monotonically to the final value of 80°. At 1400°C, wetting takes place immediately after drop deposition with a fast decrease in the contact angle to 76°. The solidified Al/ZrB 2 couples were studied by scanning and transmission electron microscopy coupled with x-ray energy diffraction spectroscopy. Structural characterization revealed that only in the Al/ZrB 2 couple produced at the highest temperature of 1400°C new phases (Al 3 Zr, AlB 2 and a-Al 2 O 3 ) were formed.