A highly effective and mild protocol for ring opening of epoxides with NH4SCN in the presence of catalytic amount of a multisite phase-transfer catalyst,α,α′,α″-N-hexakis(triethylammoniummethylene chloride)-melamine,is developed.A variety ofβ-hydroxy thiocyanates as important intermediates in agricultural and pharmaceutical chemistry were obtained in high yields with excellent regioselectivity and in short reaction times. A highly effective and mild protocol for ring opening of epoxides with NH4SCN in the presence of catalytic amount of a multisite phase-transfer catalyst, α, α ’, α "-N-hexakis (triethylammoniummethylene chloride) -melamine, is developed. of β-hydroxy thiocyanates as important intermediates in agricultural and pharmaceutical chemistry were obtained in high yields with excellent regioselectivity and in short reaction times.