The catalytic asymmetric allylation reaction involving allylboron species has emerged as a powerful tool to access highly stereoselective allylation products. In the early years, most of the researches focused on the reaction of unsubstituted allylboronates with ketones or imines. With the synthesis of complex substituted allylboronates, allylboronic acids and allyltrifluoroborates, the type of reactions and the variety of substrates are greatly expanded. Therefore, this review article will emphasize on the aspect of regio- and stereoselectivity when substituted allylboron species involving and their application on the construction of versatile organic building blocks, drugs and natural products.