Aryl borates lie at the heart of carbon–carbon bond couplings, and they are widely applied to the synthesis of functional materials, pharmaceutical compounds, and natural products. Currently, synthetic methods for aryl borates are mostly limited to metal-catalyzed routes, and nonmetallic strategies remain comparatively underdeveloped. Herein, we report a mild, scalable, visible-light-induced cross-coupling between aryl dibenzothiophenium triflate salts and bis­(catecholato)-diboron for the construction of C–B bonds in the absence of base, transition metal–ligand complex, or photoredox catalyst. Mechanistic studies reveal that this transformation is achieved through an electron donor–acceptor (EDA) complex activation in the absence of a catalyst. The mild reaction conditions allow the preparation of aromatic borates in good yields with excellent functional group tolerance. This photochemical protocol was also successfully applied to the late-stage modification of natural products and the synthesis of a drug intermediate, greatly demonstrating broadened utility.