Magnetron sputtered TiNi thin films usually exhibit an amorphous structure and need a high substrate temperature (>450 °C) or a post-annealing treatment (>500 °C) to promote crystallization. However, these treatments could extremely limit the use of low melting point substrate materials. In this study, TiNi thin films were prepared by HiPIMS using different deposition parameters. The structure and phase transformation of TiNi films were investigated. Based on SEM, XRD, TEM, DSC and electrical resistivity analysis, results show that it is possible to deposit dense crystalline TiNi thin films at a low substrate temperature (230 °C). The crystallization mechanism was also discussed. Ions energy and substrate temperatures significantly affected the formation of crystalline structures.