The early precipitation process of Ni(75)Al(14)Mo(11) alloy was simulated by microscopic phase-field model at different temperatures.The microstructure of the alloy,the precipitation time of Llo structure and occupation probability of the three kinds of atoms were investigated.It is indicated that the non-stoichiometric Ll0(Ⅰ/Ⅱ) phases are found in the precipitation process.With the temperature increasing,the appearance time of Ll0 is brought forward.The Ll0(Ⅱ) structure always precipitates earlier than the Ll0(Ⅰ) structure.Compared with lower temperature,higher temperature brings the formation time of Ll0 phase forward and makes Ll0 phase have a higher order degree.But lower temperature shortens the process time of the Ll0 phase to the Ll2 phase.Al and Mo atoms tend to occupy γ site,Ni atom tends to occupy a and β sites.At the same temperature,Al atom has stronger occupation ability than Mo atom in the same site.Ni,Al and Mo collectively form the composited Ll2 structure.