The preparation of bimetallic rhodium-germanium/silica and rhodium-germanium/alumina catalysts was investigated by controlled surface reaction. Their catalytic performances were measured for two gas phase reactions (toluene hydrogenation at 323 K and cyclohexane dehydrogenation at 543 K) and for a liquid phase reaction (citral hydrogenation at 343 K). Elemental analysis of bimetallic catalysts showed that germanium can be deposited by redox reaction between hydrogen activated on a parent monometallic rhodium catalyst and germanium tetrachloride dissolved in water (catalytic reduction method). EDX microanalysis of rhodium-germanium/silica catalysts indicated that rhodium and germanium were deposited in close contact on the silica support. However, on alumina-supported catalysts, germanium deposition occurred also separately on the support. For the different test reactions, the catalytic properties of rhodium were strongly altered by the addition of Germanium. On alumina-supported catalysts, interesting catalytic effects were observed in citral hydrogenation when not only close contact exists between both metals but when, in addition, the second metal was deposited on the support in the close vicinity of rhodium.