Novel polyaniline nanofibers/carbon nanotubes hollow cages were prepared via the layer-by-layer assembly technique on spherical templates. For the first time, we reported a facile and efficient method to stabilize the hollow structure by in situ polymerization of aniline. After that, the hollow cages were changed to be hollow microspheres, with the morphology transferred from collapsed one to free-standing one. Moreover, the shell thickness obviously increased. Raman spectra revealed that there were not only electrostatic interaction but also pi-pi conjugation between the polyaniline nanofibers and carbon nanotubes, and also demonstrated that the formative polyaniline resulted in the more stable structure. The maximum specific capacitance of the final product was calculated to be 514 F g(-1) and 94% of its original specific capacitance remained after 500 cycles, indicating that it is a promising electrode material for high performance supercapacitors. (c) 2013 Elsevier Ltd. All rights reserved.