One-dimensional (1D) ZnO/4-mercaptopyridine (4-Mpy)/Ag assemblies have been prepared by immersing ZnO rod arrays modified by 4-MPy into Ag nanoparticles colloid. Scanning electron microscopy (SEM). Raman spectroscopy and X-ray photoelectron spectroscopy (XPS) have been employed to investigate the formation process of ZnO/4-Mpy/Ag assemblies. It shows that 4-Mpy molecules are adsorbing on the surface of the ZnO rod arrays, then 4-Mpy molecules are partially dissociated from ZnO rod arrays by desorption and connect with Ag nanoparticles via the S atom. The analysis of XPS confirms the result obtained from Raman spectra of ZnO/4-Mpy/Ag assemblies. This research provides a direct spectroscopic evidence for the formation of mixed 1D ZnO/4-Mpy/Ag assemblies. (C) 2010 Elsevier Inc. All rights reserved.