A novel method is developed to increase the resistance to electrochemical carbon corrosion using a self-assembled organosilane coating of dodecyltrichlorosilane (DTS) on carbon black (CB). This process successfully creates a hydrophobic coating on the hydrophilic surface of carbon black without poisoning Pt nanoparticles. The hydrophobic DTS coating improves the performance of CB in fuel cells by enhancing the mass transfer rate. Following carbon corrosion tests, on-line mass spectrometry shows that this DTS coating improves the electrochemical carbon corrosion resistance of CB by increasing the contact resistance of water, which is necessary for electrochemical carbon corrosion. Thus, this DTS coating is a very effective means to improve the performance and durability of fuel cells.