The crystallographic texture, orientation relationships, coherency stress, and thermal stability of sputter-deposited Ni/Ni 3 Al multilayered thin films were studied as a function of bilayer period (⌳) as well as processing parameters such as substrate type, deposition temperature, and prebake conditions. Deposition onto oxidized Si or single-crystal Cu(001), NaCl(001), or KBr(001) substrates near room temperature produces multilayers with a [111] crystallographic texture along the Ni/Ni 3 Al interface normal and a disordered face-centered cubic structure for the Ni 3 Al phase. In contrast, deposition at 673 K onto NaCl(001) or KBr(001) substrates that are prebaked in vacuum at 693 K produces a chemically ordered L1 2 structure for the Ni 3 Al phase and (001) epitaxial growth. X-ray diffraction measurements of (001) multilayers with equal volume fraction of Ni and Ni 3 Al reveals a transition from a nearly incoherent state at ⌳ ס 240 nm to a semicoherent one at ⌳ ס 40 nm. Remarkably, (001) multilayers were observed to solutionize at 1373 K, which is approximately 100 K below that predicted by the Ni-Al phase diagram.