Here, we demonstrated a transition metal-mediated/monophosphorus ligand system for the selective synthesis of ketones or chiral allylic alcohols in high yields/enantiomeric excess from the 1,2-addition of arylboronic acids to α,β-unsaturated aldehydes. Notably, isomerization of the chiral allylic alcohols to ketones was suppressed by the Ru-catalyzed/monophosphorus ligand system. The asymmetric catalytic system provides an alternative and efficient method of preparing chiral allylic alcohols.