A simple silver salt (AgOAc)-catalyzed anti-Markovnikov-selective hydroboration of alkenes, 1,3-dienes, and alkynes with pinacolborane (HBpin) has been described. This strategy provides an efficient and practical method to access various alkyl-, allyl-, and ( E)-alkenylboronate esters in good to excellent yields with regio- and stereoselectivity under ligand- and base-free conditions.