The influence of calcination temperature on copper spatial localization in Y-stabilized ZrO2 powders was studied by attenuated total reflection, diffuse reflectance, electron paramagnetic resonance, transmission electron microscopy, electron energy loss, and energy-dispersive X-ray spectroscopies. It was found that calcination temperature rise in the range of 500–700 °C caused the increase of copper concentration in the volume of ZrO2 nanocrystals. This increase was due to Cu in-diffusion from surface complexes that contained copper ions linked with either water molecules or OH groups. This copper in-diffusion led also to an enhancement of absorption band peaked at ~270 nm that was ascribed to the formation of additional oxygen vacancies in nanocrystal volume. Further increasing of calcination temperature from 800 up to 1000 °C resulted in outward Cu diffusion accompanied by a decrease of the intensity of the 270-nm absorption band (i.e., oxygen vacancies’ number), the transformation of ZrO2 tetragonal (cubic) phase to monoclinic one as well as the enhancement of absorption band of dispersed and crystalline CuO in the 600–900 nm range.