For several simple alcohols such as methanol, ethanol, 1-propanol, 1-butanol, and 1-pentanol, physical properties of the microlayers of the new-type ionic liquids generated during the electrode processes of these undiluted redox liquids were studied. In all cases, well-reproducible, transport-controlled, anodic voltammograms were obtained at Pt microelectrodes. It has been found that the transport properties of the undiluted alcohols, such as activation energy of diffusion and diffusion coefficients, are strongly affected by the enormously large concentration of ions in the region adjacent to the electrode surface. The results obtained for alcohols were compared to those of diluted 1,1 ' -ferrocenedimethanol, which compound may be treated as a model redox system. This comparison revealed, in contrast to the Stokes-Einstein relation, that the molecules of each alcohol, while having much smaller size, than the molecules of 1,1 ' -ferrocenedimethanol, diffuse to the microelectrode surface at a similar rate (methanol) or slower (other alcohols). In the sequence from methanol to 1-pentanol the ratio of diffusivities of alcohol and 1,1 ' -ferrocenedimethanol ranges from 1.16 to 0.62. This may serve as evidence for the formation of a very viscous ionic layer at the electrode surface during the electrolysis of undiluted alcohols. It has also been found that the ionic layer formed during the electrode process of the undiluted alcohol is much more dense than the solvent in the bulk. This difference in densities engenders an extra transport of natural convective (gravitational) character and influences the voltammetric wave heights. For example, at a 25-mum-in-radius electrode, positioned horizontally, natural convection accounts for 10.5, 7, and 5.5% of the total current for methanol, 1-propanol, and 1-pentanol, respectively. The gravitational effect becomes negligible for the electrodes smaller than 5 mum in radius.