Carbon composite spheres with graphene oxide (GO) walls were synthesized on polymer spheres by a layer-by-layer (LbL) method using polymeric polycation solution and GO colloid solutions. The structural wall thickness of the carbon composite sphere was controlled by the number of LbL cycles. The structural wall thickness was investigated for 1-10 LbL cycles. The shape of the carbon composite sphere was uniform, and its surface morphology was similar to that of a papier-mache ball.