Orthodontic archwire rotation around its long axis, known as third-order torque, is utilised to correct tooth rotational misalignments moving the tooth root closer to or away from the cheek through engagement with an orthodontic bracket. Studying the behaviour of archwire and brackets during an applied rotation can aid in better understanding and appreciating the mechanics of third-order torque, potentially allowing for more effective orthodontic treatment protocols. Mechanically characterising archwire behaviour during third-order torque application is a complex task due to their physical scale and geometries. An advanced measurement technique was needed to address these constraints. A three-dimensional (3D) non-contact optical method using a digital image correlation (DIC) system was developed. An orthodontic torque simulator (OTS) was used to apply and measure third-order torque with 0.483 × 0.635 mm (0.019″ x 0.025″) rectangular archwires in tandem with a 3D DIC system, whereby surface deformations and strains could be computed using correlation algorithms. The 3D DIC system was implemented to enable third-order torque experimentation with the OTS while imaging the archwire and bracket surfaces. The 3D DIC system's ability to measure 3D archwire deformations and strains was verified using a finite element model, where comparisons between 3D DIC measurements and calculated results from the model were made to ensure the measurement capabilities of 3D DIC in the context of third-order torque. The 3D DIC system was then used to compare archwire behaviour between stainless steel (SS) and titanium molybdenum alloy (TMA) archwires to study potential clinical differences in archwire behaviour, in which the archwires were rotated with a custom SS rigid dowel (RD) as well as commercial Damon Q orthodontic brackets. The quantification of third-order torque and archwire deformations and strains led to the conclusion that SS archwires led to larger torque magnitudes compared to TMA archwires. The RD resulted in larger archwire strains compared to Damon Q brackets. The 3D DIC system provides a non-contact measurement technique that can further be used with third-order torque experimentation with the OTS.