Cyclic and bicyclic sulfates have been prepared from commonly available alcohols. Nucleophilic cleavage of the cyclic sulfates affords a new type of water-soluble mono- and ditertiary phophines bearing -OSO3Li groups in distinguished positions in the molecular framework. Both phosphines have amphiphilic character. Reactions of the chiral 2 and the dppp analogue 5 with [Rh(COD)Cl]2 and Pt(PhCN)2Cl2 provide novel zwitterionic complexes. Rhodium complexes of 2 and 5 have been successfully applied in liquid biphasic hydroformylation of styrene and octene-1. When the rhodium complex of 5 was used as catalyst in hydroformylation of styrene, less then 4 ppm rhodium could be detected in the organic phase.Key words: cyclic sulfates, water soluble phosphines, amphiphilic character, Rh complexes, Pt complexes, hydroformylation.