This paper presents a new and more sustainable alternative approach for the Sharpless catalytic asymmetric dihydroxylation (AD) of olefins using a water/surfactant system as reaction media. The AD reaction was performed using several cationic and anionic surfactants allowing yields and enantiomeric excesses higher or comparable with the conventional systems (using organic mixtures). The use of this water/surfactant medium offers the additional advantage of performing the reactions without the need of a slow addition of olefins. Asymmetric dihydroxylation of 1-hexene in a 1.5 mM sodium cholate aqueous solution, using N-methylmorpholine N-oxide (NMO) as co-oxidant was selected as model system to evaluate the feasibility of recycling the Sharpless catalytic system by nanofiltration. The reaction media was processed by nanofiltration, the product was isolated in the permeate, whereas the catalytic system and surfactant were retained by the membrane and recycled through six successive reactions, improving the catalyst turn-over number. The experimental results were compared with the ones calculated on the basis of mass balances, membrane rejections to product and reaction yields.