2-Ferrocenyl-2-decanol(FcOHC10), 2-ferrocenyl-2-tetradecanol (FcOHC(14)), and 2-ferrocenyl-2-octadecanol (FcOHC(18)) were synthesized and evaluated as electrochemical probes for the behavior of alcohols in micellar solutions and microemulsions. One-electron oxidations of the ferrocene moieties were nearly reversible and controlled by diffusion in microemulsions. The electrode reactions were more complex in micellar solutions and were influenced by diffusion, adsorption onto the electrode, and possibly chemical reactions coupled to electron transfer. Amphiphilic ferrocene alcohols were reasonably informative electrochemical probes in bicontinuous microemulsions made with cationic and anionic surfactants. Apparent diffusion coefficients suggested that the alcohols are distributed between the oil-water interfaces and the oil phase of the microemulsions, with increases in chain length favoring binding at this interface. Little evidence was found for adsorption of any ferrocene alcohols at any electrode-microemulsion interface. In comparison to microemulsions of cationic surfactants, the ferrocene alcohols were more easily and rapidly reduced in an SDS microemulsion. This may be attributed to Coulombic interactions between the ferricinium oxidation product and dodecyl sulfate.