This study investigates the photoinduced C-X borylation reaction of aryl halides by forming a halogen-bonding (XB) complex using 2-naphthol as an XB acceptor. The method is chemoselective and broadly functional group tolerant and provides concise access to corresponding boronate esters. Mechanistic studies reveal that forming the XB complex between aryl halide and naphthol acts as an electron donor-acceptor complex to furnish aryl radicals through photoinduced electron transfer.