The wetting, reactivity, and phase formation at the liquid Ni-Al/TiB2 ceramic interfaces have been investigated at the temperatures close to the Ni-Al liquidus line. The wetting kinetics has been studied by the sessile drop technique utilizing liquid drop dispension and high-speed high-resolution video imaging. It is established that the wetting behavior changes from a nonreactive for the Al-rich melts to a dissolution-reactive for the Ni-rich melts. For the Ni concentration 40at.%, TiB2 precipitates are found in the solidified Ni-Al droplets after the high-temperature interaction of the melts with TiB2 substrates. Besides, new (Al,Ti)Ni-3 and (Al,Ti)(2)Ni21B6 phases are formed due to dissolution of TiB2 ceramic in Ni-rich melts and subsequent solidification.