Three mol% yttria-stabilized tetragonal zirconia polycrystals (3Y-TZP) with 0.5 wt% of magnesium oxide (MgO) and 6 wt% of molybdenum (Mo) were prepared by the pressureless sintering process, and the friction and wear behavior of the ceramic composite were studied against the alumina disc. Tribological tests were carried out both at room temperature as well as at an elevated temperature (500 °C). The result revealed that a substantial reduction of ∼50% in the friction coefficient and ∼31% reduction in the wear rate were achieved while 6 wt% Mo was added into the 3Y-TZP matrix operational at 500 °C. No significant tribological influence was observed with the addition of Mo at the normal operating temperature. The minimum coefficient of friction and low specific wear rate were achieved because of the formation of MoO3 in between the mating surfaces at elevated temperature. The worn surfaces were characterized by means of field emission scanning electron microscopy (FESEM). The formation of MoO3 phases was identified by wear debris analysis which was performed with the help of X-ray photoelectron spectroscopy (XPS).