We report here a novel protocol for the hydroboration of alkynes and alkenes, which in the presence of neosilyllithium (LiCH2SiMe3) (5 mol %) and pinacolborane efficiently results in the formation of corresponding alkenyl and alkyl boronate ester products in good yields. The electron-donating and electron-withdrawing substituents on the aromatic rings of alkynes and alkenes converted smoothly to the desired products. When we extended the scope of reactivity to various aliphatic alkynes and styrenes using similar conditions, the alkenyl and alkyl boronate ester products were again formed in good yields. We also performed intramolecular and intermolecular reactions to check the reactivity of different functional groups on the phenyl ring. Experimental investigations and DLPNO-CCSD(T) calculations reveal mechanistic insights from the LiCH2SiMe3-catalyzed alkyne hydroboration. © 2021 Wiley-VCH GmbH