Polyetheretherketone (PEEK) is now attracting attention as an alternative to metal alloys in the dental field. In the present study, we evaluated the load-deflection characteristics of PEEK wires in addition to their frictional properties. Three types of PEEK wires are used: two sizes of rectangular shape, 0.016 × 0.022 in² and 0.019 × 0.025 in² (19-25PEEK), and rounded shape, diameter 0.016 in (16PEEK). As a control, Ni-Ti orthodontic wire, diameter 0.016 in, was used. The three-point bending properties were evaluated in a modified three-point bending system for orthodontics. The static friction between the orthodontic wire and the bracket was also measured. The load-deflection curves were similar among Ni-Ti and PEEK wires, except for 16PEEK with slot-lid ligation. The bending force of 19-25PEEK wire was comparable with that of Ni-Ti wire. 19-25PEEK showed the highest load at the deflection of 1500 μm (p < 0.05) in the case of slot-lid ligation. No significant differences were seen in the permanent deformation between Ni-Ti and all three PEEK wires (p > 0.05). No significant difference was seen in static friction between all three PEEK wires and Ni-Ti wire (p > 0.05). It is suggested that 19-25PEEK will be applicable for orthodontic treatment with the use of slot-lid ligation.