The electrooxidation of ethanol to acetate is achieved with Rh(I) diolefin amine complexes of the general formula [Rh(Y)(trop2NH)(L)] (L = PPh3, P(4-n-BuPh)3; Y = triflate, acetate; Bu = butyl) in direct alcohol fuel cells that have the peculiarity of containing a molecular anode electrocatalyst and, hence, are denoted as OrganoMetallic Fuel Cells (OMFCs). Changing the carbon black support from Vulcan XC-72 (Cv) to Ketjenblack EC 600JD (Ck) and/or the axial phosphane to produce non crystalline complexes has been found to remarkably change the electrochemical properties of the organorhodium catalysts, especially in terms of specific activity and durability. An in-depth study has shown that either Ck or P(4-n-butylPh)3 favour the formation of an amorphous Rh-acetato phase on the electrode, leading to a much more efficient and recyclable catalyst as compared to a crystalline Rh-acetate complex which is formed on Cv with PPh3 as the ligand. The ameliorating effect of the amorphous phase has been ascribed to its higher number of surface complex molecules as compared to the crystalline phase. A specific activity as high as 10 000 A gRh-1 has been found in a half cell, which is the highest value ever reported for ethanol electrooxidation.