Abstract: Hollow carbon spheres were synthesized using sulfonated polystyrene (PS) spheres as a core template and aniline monomer as carbon source. The spheres prepared were characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, Fourier infrared spectrometry, and thermogravimetry. The results showed that the as-prepared hollow carbon spheres were uniform in diameter with a shell thickness of 35nm. The morphology, diameter, and wall thickness of the hollow carbon spheres can be tuned by varying the sulfonation rate of the PS core template. Sulfonation modification of PS spheres for 8h was appropriate to prepare hollow carbon spheres. Owing to the presence of enough sulfonic acid groups on PS surface, the difference in the decomposition temperature between the PANI shells and the PS core was increased, resulting in the formation of the hollow carbon spheres with good sphericity and thick carbon shells by carbonizing sulfonated PS/PANI core-shell polymer spheres.