Glucose via acylation and bromization pathway gave acetobromo-α-D-glucose. The etherification of puerarin to 7-Hydroxyl-4′-(2,3,4,6-tetraacetyl- β-D-glucopyranosyloxy) puerarin with acetobromo-α-D-glucose was carried out in acetone in the presence of potassium carbonate. The isolated yield was 61.4% (based on puerarin). Finally, 7-hydroxyl-4′-(β-D- glucopyranosyloxy)puerarin was obtained via deacetylation in anhydrous methanol in the presence of potassium carbonate with isolated yield of 90.5%. Structures of intermediates and final product were characterized by 1H NMR spectra and MS. Compared to puerarin, the water-soluble of 7-hydroxyl-4′-(β-D-glucopyranosyloxy) puerarin was increased by 15.3 times.