Ni–25at.% Mo alloys have been successfully deposited using the laser engineered net-shaping (LENSTM) process. The feedstock used for the depositions was a blend of elemental Ni and Mo powders. The as-deposited alloy was homogeneously mixed and exhibited a metastable single phase microstructure consisting of an fcc phase with short range chemical ordering of the ‹ 1 1/2 0 ›* type. The effect of the thermodynamic enthalpy of mixing of the elemental powders on the microstructural development and rate of solidification in the alloy has been discussed in this paper.