Photoinduced borylation has emerged as a valuable strategy for synthesizing arylboronic esters. However, photochemical transformations involving inert bonds such as C(sp2)−F bonds are still challenging. Herein, we report a straightforward and operationally simple method for the activation of various inert carbon−heteroatom bonds, enabling the synthesis of diverse arylboronic esters without the need for transition metals or catalysts. Mechanistic investigations reveal that the deprotonation of DMSO plays a pivotal role in the reaction, and the excited DMSO anion can undergo electron transfer to the aryl substrates activated by anionic sp2−sp3 diboron compounds, i.e., [FB2pin2]−, thereby facilitating the cleavage of carbon−heteroatom bonds. The reaction allows the conversion of diverse Caryl−hetero bonds in batch and flow reactors into the corresponding arylboronic esters. The products can be used in a subsequent Suzuki-Miyaura cross-coupling without isolation.