This article discusses the results of transmission electron microscopy (TEM)-based investigation of nickel silicide (NiSi) thin films grown on silicon. Nickel silicide is currently used as the CMOS technology standard for local interconnects and in electrical contacts. Films were characterized with a range of TEM-based techniques along with glancing angle X-ray diffraction. The nickel silicide thin films were formed by vacuum annealing thin films of nickel (50 nm) deposited on (100) silicon. The cross-sectional samples indicated a final silicide thickness of about 110 nm. This investigation studied and reports on three aspects of the thermally formed thin films: the uniformity in composition of the film using jump ratio maps; the nature of the interface using high resolution imaging; and the crystalline orientation of the thin films using selected-area electron diffraction (SAED). The analysis highlighted uniform composition in the thin films, which was also substantiated by spectroscopy techniques; an interface exhibiting the desired abrupt transition from silicide to silicon; and desired and preferential crystalline orientation corresponding to stoichiometric NiSi, supported by glancing angle X-ray diffraction results.