By means of X-ray photoelectron spectroscopy (XPS) and differential scanning calorimetry (DSC), this study set out to investigate the application of plasma immersion ion implantation (PIII) for the surface modification of ProTaper NiTi rotary instruments. This study was undertaken because the PIII method was perceived to have the potential of developing into a standard surface modification technique that improves clinical quality and outcome. Specimens received nitrogen ion or nitrogen plus argon ion implantation. XPS analyses with and without argon ion etching were obtained for all specimens. In addition, DSC analysis was performed to investigate the phase transformation behavior of the bulk material. Results indicated that the surfaces of NiTi instruments were successfully modified by nitrogen PIII, whereby a light golden TiN layer was yielded. Moreover, the PIII technique did not alter the superelastic character of NiTi instruments because it was carried out at near-room temperature. We thus concluded that nitrogen PIII is a promising surface modification technique to improve the surface characteristics of NiTi rotary instruments.