Self-assembled monolayers (SAMs) have been widely used in studying inter-facial phenomena, biological processes, electrochemistry, photoelectrochemistry, photoactivity and molecular interaction. Much research has been carried out in fabricating and removing SAMs on different substrates. In this work, we report for the first time, to our knowledge, that SAMs of thiolates on gold can be removed by immersing SAMs in 0.5 M NaBH4 solution for 10 min. The procedure of removing thiolates was very convenient. Cyclic voltammetry, surface-enhanced Raman spectroscopy, and X-ray photoelectron spectroscopy were used to characterize this process. The results indicated that the SAMs of thiolates on gold can be removed efficiently by NaBH4..