Borylation reactions are heavily dependent on diboron agents, whose structures prescribe the reaction conditions. It necessitates extended investigation of borylation reactions using other diboron agents as a boron source than B(2)pin(2). In this work, borylation of unactivated primary and secondary alkyl halides with bis(neopentyl glycolato)diboron (B(2)npg(2)) was investigated, and a favorable catalysis system was constructed for B(2)npg(2)-based borylation reaction after probing a variety of catalysis systems composed of a copper salt, ligand, and base. The investigation showed that this boryl substitution could proceed at room temperature, producing alkylboronates with high yield. This work provides an alternative method to the synthesis of alkylboronate for further Suzuki-Miyaura cross-coupling reactions.