γ–Fe2O3 spherical particles with diameters between 5 and 3.5 nm—very uniform in size—have been prepared by laser pyrolysis of iron pentacarbonyl. The infrared spectra of the samples showed features that indicated different degrees of crystallinity according to the preparation conditions. Low saturation magnetization values (≈10 emu/g) and very high coercivities at low temperature (3000 Oe) have been found for the γ–Fe2O3 nanoparticles with the smaller particle size and the highest structural disorder. To explain the magnetic properties, it was necessary to consider additional anisotropies caused by the increase in surface and structural disorder as the particle size decreased.