Low-density self-assembled monolayers (LD-SAMs) undergo a reversible change in wetting properties in response to an external stimulus, such as light or an electric potential. This ability to externally tune wetting could provide a means of directing fluid flow in sensing devices, without the use of moving parts or a large power supply. We investigated LD-SAMs of ω–functionalized carboxylic acid thiols on gold films. Through electrochemical experiments, we have confirmed the ability of these materials to reversibly switch between two surface states in response to an applied potential. The switching of the surface properties is due to a change in the conformation of the carboxylic acid chains tethered to the surface of the gold film. Our results also show that the switching dynamics is strongly dependent on the solution composition. We have combined data obtained from electroanalytical measurements (EIS, CV, Chronocoulometry) and dynamic contact angle measurements (electrowetting) with molecular dynamic simulations to predict the response of the LD-SAMs on solution composition. In addition, we show that changing the SAM composition on the surface allows us to limit the importance of the solution composition on the switching dynamic, and also to increases the electrochemical stability of the SAM on the surface.