Potential mapping of organic thin-film transistors (TFTs) has been carried out using originally developed atomic-force-microscope potentiometry (AFMP). The technique is suitable for the accurate measurement at metal–semiconductor boundaries of working TFTs. Potential drops near metal–organic boundaries are observed for both source and drain Au top contacts of a pentacene TFT. The approximate width of the steeper potential slope is 400 nm, which is larger than the spatial resolution of AFMP. The potential drop is considered to be due to a damaged area with low carrier mobility caused by the Au evaporation, which is also reproduced by device simulation.