Quantitative metallurgical and phase analyses employing neutron diffraction technique were conducted on two as-received commercial rectangular austenitic stainless steel orthodontic archwires, G&H and Azdent, 0.43×0.64 mm (0.017×0.025 inch). Results showed a bi-phase structure containing martensitic phase (45.67% for G&H and 6.62% for Azdent) in addition to the expected metastable austenite. The former may be a strain-induced phase-transformation arising during the cold working process of wire fabrication. Further neutron resonance capture analysis determinations provided atomic and isotopic compositions, including alloying elements in each sample, complementary to the results of traditional energy dispersive X-ray spectroscopy. Together, these results assist in relating commercial alloying recipes and processing histories with mechanical performance, strength and ductility in particular.