In this work, hyperbranched azobenzene-containing polymeric diazonium salt (HB-DAS) and poly(thiophene-3-acetic acid) (PTAA) were used as building components to fabricate hollow capsules. The capsules were prepared through layer-by-layer self-assembly of the components on PS latex spheres followed by removal of the PS cores with THF dissolution. The TEM, SEM, and AFM observations confirmed that uniform hollow capsules with an average wall-thickness of 5.9 nm were obtained.