Self-assembly can be a powerful, but simple, synthetic method for the fabrication and surface modification of nanometer- to micrometer-sized hollow spheres. Here we report a facile route for preparation of submicrometer ferrite hollow spheres which are amphiphilic and superparamagnetic. This unique approach involves the formation of ferrite nanocrystals and the simultaneous self-assembly of nanocrystals and block copolymer PEO-PPO-PEO into hollow spheres. Furthermore, this approach is general for the preparation of a series of ferrite hollow spheres, including Fe3O4, Co1-xFe2+xO4, and Mn1-xFe2+xO4. Unlike conventional hollow spheres, which are either hydrophobic or hydrophilic, the products we obtained exhibit excellent dispersibility in both polar and nonpolar solvents.