We present our work on direct assembly of Ag nanoparticulate film onto mica substrates without coupling agent, and investigate the potential application of this kind of assembly to SERS. Colloidal Ag is assembled onto mica substrates treated with MnCl 2 solution by electrostatic interaction, which forms a two-dimensional submonolayer. As shown by AFM study, the assembled process is size-selective, e.g., Ag particles assembled onto mica are more uniform than the mother colloid. The as-prepared Ag nanoparticulate films were shown to be active for surface-enhanced Raman scattering(SERS), as evidenced by the strongly enhanced Raman scattering from the self-assembled films(SAMs) of p-mercaptoaniline(p-MA). We present our work on direct assembly of Ag nanoparticulate film onto mica substrates without coupling agent, and investigate the potential application of this kind of assembly to SERS. Colloidal Ag is assembled onto mica substrates treated with MnCl 2 solution by electrostatic interaction, which forms a As shown by AFM study, the assembled process is size-selective, eg, Ag particles assembled onto mica are more uniform than the mother colloid. The as-prepared Ag nanoparticulate films were shown to be active for surface-enhanced Raman scattering (SERS), as evidenced by the strongly enhanced Raman scattering from the self-assembled films (SAMs) of p-mercaptoaniline (p-MA).