The aim is to investigate the premature catastrophic fracture produced for different periods during clinical endodontic treatment of two brands of NiTi endodontic rotary instruments. 3 samples as-received, 6 samples used with patients for 2 and 7 h and 5 samples fractured were studied for each brand of endodontic NiTi rotary instruments. Transformation temperatures (Ms, Mf, As and Af) and enthalpies of transformation were determined by calorimetry. Critical stresses until fracture (σβ→SIM, σSIM→β) were obtained using an electromechanical testing machine. The samples were also visualized by Scanning Electron Microscopy. Calorimetric studies have shown an increase of the Ms and As transformation temperatures with time of use as well as a decrease of their stress transformations. Moreover, reverse transformation enthalpies decreased along the time. The enthalpies of transformation decreased because martensitic plates were anchored, which prevented their transformation to austenite; thus losing its superelastic effect. The stabilisation of the martensitic plates induced the collapse of the structure and so the main cause for the fracture. The heat treatment proposed has been increased the life in service of NiTi superelastic endodontic instruments recovering theirs superelastic effect.