In this paper, we present the facile preparation of polyaniline (PANI) hollow spheres by using a silane coupling agent, N-[3-(trimethoxysilyl) propyl]aniline (PAPTMS), as a precursor. The PANI hollow spheres exhibit tunable shell thickness. PAPTMS was used to prepare aniline-modified silica microparticles, 550 nm in diameter, by the Stober process. PANI-coated silica core-shell microcapsules (SiO2@PANI) were subsequently obtained by performing chemically oxidative polymerization of a specific aniline monomer loading in the presence of the core-shell particles. PANI hollow spheres with tunable PANI shell thicknesses were eventually obtained by immersing the as-prepared core-shell particles in 5 wt% HF aqueous solutions to simultaneously remove the silica cores and further dope the PANI shells. The as-prepared core-shell particles and PANI hollow spheres were characterized using Fourier-transform infrared (FTIR) and Si-29 nuclear magnetic resonance (NMR) spectroscopies. The surface morphologies of the core-shell particles and PANI hollow spheres were investigated using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The electrical conductivities and optical absorption spectra of the as-prepared core-shell microparticles and the PANI hollow spheres were measured using the standard four-point probe method and ultraviolet-visual (UV-Vis) absorption spectroscopy, respectively. (C) 2012 Elsevier Inc. All rights reserved.