Functionalized 2-alkyn-1-ylboronates were successfully prepared in good yields by reacting various acyclic and cyclic (iodomethyl)boronates with various alkynyllithium salts. Amongst various (iodomethyl)boronates studied, 2-(iodomethyl)-1,3,2-dioxa-4,4,5,5-tetramethylborolane provided improved chemical yields of 2-alkyn-1-ylboronates with pyran- and triisopropylsilyl-substituted alkynyllithium salts. 2-Alkyn-1-ylboronate bearing an acid sensitive structure (pyran) was successfully synthesized which would be very difficult to achieve under previously reported reaction conditions. The exceptionally rapid rearrangement of the “ate” complex derived from the pinacol (iodomethyl)boronate, suppression of the side product formation, and the stability of the pinacol 2-alkyn-1-ylboronate are some of the notable merits of this protocol. This new procedure offers a simple and convenient alternative route to the existing methodologies, in terms of the milder reaction conditions, functional group compatibility, and the ease of the operation. The synthesis scope of this class of 2-alkyn-1-ylboronates was demonstrated by reacting the pinacol 2-alkyn-1-ylboronate with benzaldehyde, which yielded the α-allenic alcohol in good yield and regioselectivity.