Undoped, Cu and/or Y doped ZrO 2 nanopowders were synthesized with Zr, Y, and Cu nitrates using a co-precipitation approach. Their structural and optical properties were examined regarding dopant content (0.1–8.0 mol.% of CuO and 3–15 mol.% of Y 2 O 3 ) and calcination conditions (400 °C–1000 °C and, 1,2 or 5 h) through Raman scattering, XRD, TEM, EDS, AES, EPR, UV–vis and FTIR diffused reflectance methods. The results showed that both Cu and Y dopants promoted the appearance of additional oxygen vacancies in ZrO 2 host, while the formation of tetragonal and cubic ZrO 2 phases was primarily influenced by the Y content, regardless of Cu loading. The bandgap of most of the powders was observed within the 5.45–5.65 eV spectral range, while for those with high Y content it exceeded 5.8 eV. The (Cu,Y)-ZrO 2 powders with 0.2 mol.% CuO and 3 mol.% Y 2 O 3 calcined at 600 °C for 2 h demonstrated nanoscaled tetragonal grains (8–12 nm) and a significant surface area covered with dispersed Cu x O species. For higher calcination temperatures, the formation of Cu Zr 2+ EPR centers, accompanied by tetragonal-to-monoclinic phase transformation, was found. For fitting of experimental FTIR reflection spectra, theoretical models with one, five, and seven oscillators were constructed for cubic, tetragonal, and monoclinic ZrO 2 phases, respectively. Comparing experimental and theoretical spectra, the parameters of various phonons were determined. It was found that the distinct position of the high-frequency FTIR reflection minimum is a unique feature for each crystalline phase. It was centered at 700–720 cm −1 , 790–800 cm −1 , and 820–840 cm −1 for cubic, tetragonal, and monoclinic phases, respectively, showing minimal dependence on phonon damping coefficients. Based on the complementary nature of results obtained from structural and optical methods, an approach for monitoring powder properties and predicting catalytic activity can be proposed for ZrO 2 –based nanopowders.