Multiforce nickel–titanium (NiTi) orthodontic archwires release progressively increasing forces in a front-to-back direction along their length. The properties of NiTi orthodontic archwires depend on the correlation and characteristics of their microstructural phases (austenite, martensite and the intermediate R-phase). From a clinical and manufacturing point of view, the determination of the austenite finish (Af) temperature is of the greatest importance, as in the austenitic phase, the alloy is most stable and exhibits the final workable form. The main purpose of using multiforce orthodontic archwires is to decrease the intensity of the applied forces to the teeth with a small root surface area, such as the lower central incisors, and also provide forces high enough to move the molars. With the optimally dosed forces of multiforce orthodontic archwires in the frontal, premolar and molar segments, the feeling of pain can be reduced. This will contribute to the greater cooperation of the patient, which is of utmost importance to achieve optimal results. The aim of this research was to determine the Af temperature at each segment of as-received and retrieved Bio-Active®and TriTanium®archwires with dimensions of 0.016 × 0.022 inches, investigated by the differential scanning calorimetry (DSC) method. A classical Kruskal–Wallis one-way ANOVA test and multi-variance comparison based on the ANOVA test statistic using the Bonferroni corrected Mann–Whitney test for multiple comparisons were used. The incisor, premolar and molar segments have different Af temperatures, and they decrease from the anterior to posterior so that the posterior segment has the lowest Af. Bio-Active®and TriTanium®with dimensions of 0.016 × 0.022 inches can be used as first leveling archwires by additional cooling and are not recommended for use on patients with mouth breathing.