Periodic multilayered titanium-rich Ni-Ti thin films were prepared by magnetron sputtering from alternating Ni45Ti50Cu5 alloy and pure titanium targets, with an alloy-layerfl'i-layer thickness ratio of 9:1. The microstructure, martensite transformation behavior, and precipitate and defect structures were studied in films which had been annealed at 923K for one hour and furnace cooled at <20 K/min. Energy dispersive X-ray fluorescence measurements showed that the resulting films had a hyperstoichiometric titanium content of approximately 51 atomic percent. Ti2Ni precipitates were found in the annealed structures which were oriented with [1 1 0 ]Ti2Ni parallel to B2 and (001)Ti2Ni parallel within +/− 10 to (001)B2. Differential scanning calorimetry (DSC) revealed an unusually low transformation enthalpy for the martensite reaction in the film (9.1 J/g as opposed to 20.7 J/g for the alloy sputtering target), and a significant fraction of residual B2 austenite was found at temperatures well below the nominal Mf. The martensite transformation was found to occur in two steps involving, on cooling, the initial formation of an orthorhombic martensite prior to transformation to the monoclinic martensite phase at low temperature.