The structure of Ni–20at.% Mo and Ni–25at.% Mo alloys heat treated at different temperatures was studied by the method of transmission electron microscopy. X-ray photoelectron spectroscopy was used to detect the sign of the chemical interaction between Ni and Mo atoms at different temperatures. It is shown that at high temperatures the tendency toward phase separation takes place. The system of additional reflections at positions {1½0} on the electron diffraction patterns testifies that the precipitation of crystalline bcc Mo particles begins in the liquid solution. At 900°C and below, the tendency toward ordering leads to the precipitation of the particles of the chemical compounds. A body-centered tetragonal phase Ni 4 Mo (D1 a ) is formed in the Ni–20at.% Mo alloy. In the Ni–25at.% Mo alloy, the formation of the Ni 3 Mo (D0 22 ) chemical compound from the A1 solid solution has gone through the intervening stage of the Ni 4 Mo (D1 a ) and Ni 2 Mo (Pt 2 Mo) formation.