A detailed Zr-91 NMR investigation is presented of the five component (cubic, monoclinic, tetragonal, orthorhombic and (delta) phase mixture in the transformation toughened engineering ceramic, magnesia-partially-stabilised zirconia (MgPSZ). The phases are distinguished on the basis of the quadrupole interaction displayed in the powder pattern of the Zr-91 (1/2, -1/2) transition. This paper reports: (i) the first characterisation of the magnesia-fully-stabilised cubic phase at the eutectic composition (13.5 mol% MgO); (ii) the observation of a poorly ordered tetragonal phase on fast cooling ZrO2 (9.3 mol% MgO) from the cubic phase field at 1720 degrees C, and the subsequent growth and ordering of the tetragonal phase precipitates due to further annealing; (iii) the observation of the (partial) transformation of the cubic phase to the ordered delta-phase (Mg2Zr5O12) on annealing MgPSZ at 1100 degrees C for 8 h; and (iv) the observation of the transformation of the tetragonal phase into the orthorhombic phase after cooling in liquid nitrogen, and the reverse transformation after heating to 600 degrees C.