We demonstrate an efficient method for the hydroboration of terminal alkenes or alkynes with pinacolborane (HBpin) using the aluminium catalyst, [κ2-{Ph2P(=Se)NCH2(C5H4N)}Al(CH3)2] (1), supported by a functionalized amidophosphine ligand under mild and solvent-free conditions to afford the corresponding alkyl and alkenyl boronate esters in high yield. This protocol involves the chemoselective formation of an anti-Markovnikov product exclusively. Both terminal alkenes and alkynes bearing a wide array of electron-withdrawing and donating functional groups can easily be converted to the corresponding product through the formation of aluminum hydride as an active catalytic species. © 2019 The Royal Society of Chemistry and the Centre National de la Recherche Scientifique.