Two new phosphines, Tris[p-(10-phenyldecyl)phenyl]phosphine and 2,2＇-Bis{di[p-(10-phenyldecyl)phenyl]phosphinomethyl} -1,1＇-biphenyl were successfully synthesized and sulfonated in concentrated H2SO4. The resulting water soluble surface active phosphines were applied to the rhodium catalyzed hydroformylation of higher olefins. It is found that these two ligands are not only excellent for octene hydroformylation, but catalyze tetradecene hydroformylation under two phase conditions as well. Rates and selectivities are superior to TPPTS modified rhodium catalysts under the same reaction conditions.