Generations 1 to 3 of dendrimers ended by water-soluble phosphines are synthesized and their ruthenium complexes are used as catalysts in aqueous media; a slightly positive dendritic effect on the regioselectivity is observed for hydration of alkynes and a large positive dendritic effect is observed in the biphasic (water/heptane) catalysed isomerisation of allylic alcohols to ketones where the products are easily isolated and the catalyst can be reused several times, even the first generation.