We report here a preparation for thin gold films on mica substrates. We have investigated the influence of the substrate temperature and the evaporation rate on the morphology of the films. After careful outgasing of the substrate, 100 nm of Au is evaporated onto the mica surface maintained at high temperature. After slow cooling, ex situ characterizations are performed using AFM and STM. For our purposes, the best compromise between roughness and grain size is found to occur for an evaporation rate of 2 ˚ A s −1 onto a mica substrate maintained at 460 • C. We have used these substrates for STM and AFM study of decanethiol self-assembled monolayers (SAMs). We present results for gold samples immersed for a few seconds in decanethiol solutions, revealing an incomplete organization of the films. The organization process is discussed through comparison between AFM and STM data recorded on the SAMs. Then we present molecular resolution STM pictures of ordered SAMs for longer immersion times.