Self-assembled poly(o-methoxyaniline) (POMA) hollow nanospheres were prepared in a solution of poly(methyl vinyl ether-alt-maleic acid) (PMVEA) by oxidative polymerization using ammonium persulfate as the oxidant. The weight ratio of PMVEA to o-methoxyaniline in the solution had a significant effect on the morphology of the poly(o-methoxyaniline) nanospheres as determined by scanning electron microscopy. The diameter of the hollow nanospheres decreased from 440 to 210 nm with an increase in the PMVEA concentration from 1% to 5%. Freeze-fracture transmission electron microscopy results showed the presence of spherical micelles composed of PMVEA/ o-methoxyaniline prior to polymerization, which also decreased in size as more PMVEA was added to the solution, and can act as soft templates for the formation of the hollow POMA nanospheres. The POMA/PMVEA hollow nanospheres were characterized by means of Fourier transform infrared, UV-visible, x-ray photoelectron spectroscopy, elemental analysis and conductivity measurements.