The reaction of yttrium acetate hydrate in 1,2-propanediol (1,2-PG) at 300 °C yielded the products containing the acetate groups and the glycol moieties. The products decomposed into Y 2O 3 below 400 °C, and the thus-obtained Y 2O 3 samples had quite large surface areas (>200 m 2/g) and were comprised of crystalline nano-hollow spheres with the outer diameter of 7–18 nm and the inner diameter of 2–8 nm. Dy 2O 3, Er 2O 3 and Yb 2O 3 composed of nano-hollow spheres were also obtained by the glycothermal treatment and subsequent calcination.