Nano-sized yttria (Y2O3) powders were synthesized by a polymer solution route using polyvinyl alcohol (PVA) as an organic carrier. The PVA polymer affected the dispersion of yttrium ions in precursor sol. In this study, three kinds of PVA polymer (different molecular weight) were applied for synthesis of yttria powder. The PVA type as well as calcination temperature had a strongly influence on the particle morphology. Single crystal nano wire particles were observed at the temperature of polymer burn out range and the size was dependent on the PVA type. The stable, fully crystallized yttria powder was obtained through the calcination at 800°C for 1 h. The yttria powder prepared with the high weight PVA (MW: 153,000) revealed a particle size of 30 nm with a surface area of 18.8 m2/g.