An efficient I2-DMSO reagent system-mediated multicomponent reaction strategy for the synthesis of C3-sulfenylated chromones from o-hydroxyaryl methyl ketones, rongalite, and dimethyl sulfoxide has been developed. Notably, the double C-S bond cleavages of rongalite and dimethyl sulfoxide served as key steps in this smooth transformation, affording the C1 unit and sulfur source for the assembly of C3-sulfenylated chromones. Preliminary mechanistic studies indicated that in situ generated HCHO and (2-(2-hydroxyphenyl)-2-oxoethyl)dimethylsulfonium iodine were probably the key intermediates in this transformation.