New water-soluble, N-heterocyclic carbene (NHC) or mixed NHC/tertiary phosphine complexes [RhCl(cod)(sSIMes)], Na2[Rh(bmim)(cod)(mtppts)], and [Rh(bmim)(cod)(pta)]BF4 were synthetized and applied for the first time as catalysts in redox isomerization of allylic alcohols in aqueous media. [RhCl(cod)(sSIMes)] (with added sulfonated triphenylphosphine) and [Rh(bmim)(cod)(pta)]BF4 catalyzed selectively the transformation of allylic alcohols to the corresponding ketones. The highest catalytic activity, TOF = 152 h−1 (TOF = (mol reacted substrate) × (mol catalyst × time)−1) was observed in redox isomerization of hept-1-en-3-ol ([S]/[cat] = 100). The catalysts were reused in the aqueous phase at least three times, with only modest loss of the catalytic activity and selectivity.