An effective approach for monodesulfonation of polyphenol sulfonate under ultrasonic irradiation was reported. Series of substituted ortho-, meta- or para-hydroxylphenol sulfonates or 5-hydroxy-1,3-phenylene bis(4-methylbenzenesulfonate) were obtained specifically in the presence of sodium hydroxide in acetonitrile. With treatment of potassium carbonate in alcohol, alkyloxylphenol sulfonates was provided via one-pot monodesulfanation followed by alkylation under ultrasonicated solvent-free conditions. The alcohol had been re-garded as green alkylation reagent. The results of the exploration of the scalability of monodesulfonation and one-pot monodesulfona-tion-alkylation of resorcinol bissulfonate indicated that such modes had the potential application value in scale production.