Inner doped polystyrene capsules are required to meet the demand of the characterization of implosion interface, the elemental content, especially the doped elemental content is the key point to the performance. In this paper, the outer and inner surface structures of the polystyrene capsule doped with sulfur were analyzed by SAXPS technique, the analyzed area was 150 mm in diameter. The results show that sulfur exists in the inner surface of the polystyrene capsule, which is consistent with the capsule producing techniques.