In this work we synthesized rare earth-doped yttria nanocrystals via the Pechini method. We used Ce(3+), Yb(3+) and Er(3+) as dopant ions and studied their behavior when they are simultaneously embedded in the yttrium oxide lattice. The tri-doped system exhibits both downshifting and up-converting properties, due to the presence of, respectively, cerium-erbium and ytterbium-erbium couples. Efforts were put into determination of the effects of the presence of increasing content of cerium. We synthesized a series of samples having the general formula (Y0.88-xCexYb0.1Er0.02)2O3, where x = 0.01, 0.02, 0.10, 0.20, and 0.40. The structural properties of the samples were analyzed by the X-ray powder diffraction (XRPD) technique and the morphological features were disclosed using transmission electron microscope (TEM) observations. Photoluminescence properties were tested by carrying out photoluminescence (PL) emission, photoluminescence excitation (PLE) and lifetime (LT) measurements.