Structural studies of Cu-doped zirconia samples with varying Cu content have been carried out. Copper–zirconia samples containing 2–20 mol% Cu were prepared by the co-precipitation technique using tetramethylammonium hydroxide as the precipitating agent and calcined at 773 K in air. The powder XRD data following Rietveld refinement revealed stabilization of zirconia in both tetragonal and cubic phases for all the samples with some monoclinic impurity phase. A decrease in the unit cell parameters of the cubic and tetragonal phase indicates incorporation of copper in the zirconia lattice of both the phases. An increase in the copper concentration (up to 20 mol%) stabilizes zirconia into the cubic phase at the expense of the tetragonal phase, with a decrease in the crystallite size (6–8 nm). Rietveld refinement of the high temperature XRD data reveals that both cubic and tetragonal phases exist up to 723 K with the cubic phase dominating (80% at 723 K). At temperature higher than 723 K, cubic phase gets transformed into the tetragonal phase, which further transforms into the monoclinic phase at 1173 K. At 1173 K, copper comes out of the cubic zirconia lattice forming a separate copper oxide phase and only the tetragonal and monoclinic polymorphs of zirconia exist.