Site-selective borylation of simple arenes was realized in one pot via an electrophilic thianthrena-tion/Pd-catalyzed borylation sequence.The key to achieve this operatically simple process is the use of Pd catalysis,which could tolerate the solvent and acidic conditions used in the thianthrenation step.This protocol features mild conditions,broad functional group tolerance,and simple manipulations,and is suitable for late-stage functionalization of a wide range of pharmaceuticals and complex bioactive molecules.