The passivity and breakdown of passivity of 1018 carbon steel in propylene carbonate (PC) and 1,2-dimethoxyethane (DME) mixtures with 0.5 molar lithium hexafluoroarsenate supporting electrolyte were examined via several electrochemical and surface analytical methods. The PC-DME/0.5 M LiAsF6 mixtures ranged from 10 to 90 mol % PC. The results from the PC/DME mixtures were compared to passivating mechanisms found in pure PC and DME solutions. In PC-rich mixtures, the breakdown of passivity occurred near the oxidation potentials of either organic solvent. Premature breakdown of the carbon steel in PC-DME mixtures occurred at sulfide inclusions as was observed earlier in PC/0.5 M LiAsF6 solutions although passive films attempted to form at these inclusion sites in mixtures containing at least 10 mol % DME. As the DME content increased in the PC-DME mixtures, the passive films formed on bare steel surfaces possessed an increasing polymer film character. In 50 and 70 mol % DME solutions nonprotective polymer films were formed. The nonprotective nature of these films indicated that PC passivation mechanisms competed and interfered with the DME mechanism of electropolymerized film formation. Only in 10 mol % PC-90 mel : % DME mixtures were.protective electropolymerized films formed on 1018 carbon steel.