Direct dimesitylborylation of benzofuran derivatives by a C−H activation catalyzed by an iridium(I)/N‐heterocyclic carbene (NHC) complex in the presence of Ph2MeSi‐BMes2 afforded the corresponding dimesitylborylation products in good to high yield with excellent regioselectivity. This method provides a straightforward route to donor–(π‐spacer)–acceptor systems with intriguing solvatochromic luminescence properties.