The aim of this study was to assess the role of the crystallographic phase of Nickel-titanium (NiTi) rotary instruments in determining their torsional resistance during different bending conditions, such as different degrees and angles of curvature. 200 F-One 20.04 instruments (Fanta Dental, Shanghai, China) were used, 100 austenitic instruments and 100 martensitic instruments. Each group was divided in 5 subgroups according to the different bending conditions (straight canal, 90° or 60° of curvature degrees and 3 mm or 5 mm of radius of curvature). The static torsional test was performed by using a device composed of an electric motor capable of recording torque values (N·cm); a vice used to secure the instruments at 3 mm from the tip; and artificial canals, which allow instruments to remain flexed during test. Each instrument was rotated at 500 rpm with a torque limit set to 5.5 Ncm until its fracture. Torque at Fracture (TtF) was registered. A scanning electron microscopy (SEM) observation was conducted. The collected data confirm that an increase in the angle of curvature and a decrease in the radius of curvature of the artificial canals lead to an increase of TtF values with a statistically significant difference (p < 0.05), both in the austenitic and martensitic groups. Regarding the comparison between austenitic and martensitic groups in the same bending condition, a statistically significant difference was found only when the torsional test was performed in the canals with the degrees of curvature of 90° and the radius of curvature of 3 mm and 5 mm, with the austenitic instruments showing a higher TtF than the martensitic ones. In conclusion, it can be stated that the crystallographic phase influences the maximum torque at fracture when the instruments are subjected to severe bending and that the radius of curvature significantly influences their torsional resistance.