Non-metal-catalyzed C-H borylation of arenes represents a sustainable and environment-friendly approach for the functionalization of arenes. Despite its promise as an alternative to traditional transition-metal systems, its substrate scope is generally limited to electron-rich arenes, thus hindering its application in organic synthesis. Herein, we report the development of a borenium-ion catalyst which can borylate unactivated arenes under ambient conditions with 4-chlorocatecholborane (HBcatCl) as borylation reagent. This metal-free catalytic system is suitable for the borylation of C-H bonds in sterically encumbered positions, which has been a challenging task for transition-metal systems. Additionally, this catalytic system allows para-selective one-pot borylation of phenols, which has not been achieved by using transition-metal systems. Our mechanistic investigations and computational studies support a synergistic activation of the H-BcatCl bond by the arene substrate and the borenium-ion catalyst. This generates a Wheland intermediate and a neutral hydroborane species and is followed by deprotonation of the Wheland intermediate with the hydroborane species. The latter step of C-H bond cleavage is likely the rate-limiting step.