In this study, we present the effect of the plasma deposition parameters on the electrical and structural properties of Ti/TiN multilayers. The films were formed by r.f. magnetron sputtering (13.56 MHz) under nitrogen and argon reactive plasma at low pressure. The first step of our study was the optimization of the deposition conditions in order to obtain good-quality films. The total pressure was set between 2 and 10 mTorr. The primary result is that the self-bias voltage plays a major role in the structural evolution of TiN films by changing the preferred film orientation and their hardness. The variation of the resistivity as the function of substrate bias was also investigated. The deposited multilayers were characterized by X-ray diffraction (XRD), energy dispersive spectroscopy (EDS), and Raman scattering analysis, as well as by the standard four-probe technique.