A carboxylic acid-directed regioselective hydroarylation reaction of unactivated alkenes with aryl boronic acids was reported. This transformation was enabled by homogeneous manganese catalyst MnBr(CO)5 in the presence of KOH and H2O in the m-xylene reaction medium. Both internal and terminal alkenes worked well in this transformation, and a series of functional groups were tolerated. This reaction not only provided an expeditious method to prepare γ-aryl carboxylic acids from simple starting materials but also would inspire further studies in employing homogeneous manganese catalysis in organic synthesis.